SAFETY AND HEALTH ISSUES
Jennifer A. Heth
37.1 INTRODUCTION
On a weekly basis, there are conflicting media
reports indicating that something is good or
bad for us, depending on the study done, the
topic and the amount of press given to it.
However, by reviewing the information and
adding common sense and moderation to our
lifestyles, we are able to discern good from bad,
thus allowing us to lead healthy and safe lives.
Working with composite materials, or any
chemicals for that matter, should be viewed in
the same manner. Know what material is used,
how it is handled, what is known about it and
how to reduce the risk of injury from any haz-
ard associated with it.
From a safety perspective, proven engineer-
ing and administrative techniques and
controls exist that can make the workplace
safe if implemented correctly. There are fairly
universal industrial hygiene protocols that
merely need to be implemented to effectively
minimize potential exposure to any hazard,
whether it be chemical or physical.
On health issues, there are numerous toxi-
cological papers published on chemicals used
in the composites industry. However, without
a toxicological background or proper analysis
and interpretation of the data, it is difficult to
know what the studies’ conclusions are and,
more importantly, if they are valid.
To assist users in understanding safety and
health issues for composite materials, the
Handbook of Composites.Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
37
Safety and Health Subcommittee of the
Suppliers of Advanced Composite Materials
Association (SACMA) researched and pub-
lished Safe Handling of Composite Materials (3rd
Edn, April 1996). This chapter is an edited ver-
sion of the booklet, with new information
added as appropriate. The information is not
meant to be inclusive. Rather, the reader
should be aware of the issues addressed and
make further investigation as needed. Note
that data cited was current in 1997.
37.2 HEALTH INFORMATION
TERMINOLOGY
It is important to understand the terminology
in order to read and assess toxicological data.
This section will concentrate on some of the
basic terms and definitions that are applicable
to the composite user, especially in reading
Material Safety Data Sheets, the most common
source of information on materials.
37.2.1 TOXIC, HAZARD AND RISK
These three words are used frequently and
sometimes interchangeably. To avoid confu-
sion, they are defined as follows.
Toxic refers to a poison or poisonous sub-
stance that may cause a harmful effect in the
body. A substance’s toxicity characteristic is a
property of the chemical, similar to its color or
odor. This is as true for chemicals like water,
salt or sugar as it is for cyanide, snake venom
or botulism toxin (Fig. 37.1).
 Health information terminology 823

Risk describes the probability or likellhood

‘All chemicals are toxic, there
are none which is not ...
\ /
The right dose differentiatesa
poison from a remedy.’
/ Paracelsus
,6th Century
that a hazard will result in a harmful effect.
Regardless of the toxicity, hazard or risk
associated with a substance, care should
always be taken to minimize exposure. This is
because what is known today may be inade-
quate compared to what tomorrow’s science
may discover (e.g. asbestos usage and asbesto-
sis or tobacco and lung cancer).

37.2.2 ACUTE TOXICITY VERSUS CHRONIC

Fig. 37.1 Toxicology principle.
Hazard takes into account the toxicity of a sub-
stance along with exposure to it. Something
can be extremely toxic, but if there is no expo-
sure, there is no hazard (Fig. 37.2). Conversely,
it is important not to be negligent in handling
low toxicity substances, as extreme exposure
(high concentration or long exposure time)
could result in high hazard.
TOXICITY
When discussing toxicity, reference will typi-
cally be made to two types: acute or chronic.
One can be instantaneous and the other mani-
fests itself over a long period of time.
Acute toxicity occurs when a harmful effect is
experienced after a single or short-term expo-
sure to a substance. It usually occurs instantly
or within a short time period. Typically, expo-
sure will be by skin or eye contact or
inhalation. In industrial settings, it would be
unlikely for exposure to be by ingestion,
though this is another route.

K = Minimal hazard
Low exposure

High toxicity

0 9- AM 6

nw
Extreme exposure
X = Elevated hazard

Low toxicity

Fig. 37.2 Risk assessment equations.

824 Safety and health issues

The most common measure of acute toxicity (possibly years or decades). Because chronic
through the oral or dermal routes is called the effects develop slowly and are measured later,
median lethal dose or LD,,. The LD,, (mg of and it is not possible to keep the workplace
chemical per kg of body weight) is the amount toxic-free, it is important to eliminate or mini-
of material that kills 50% of a group of experi- mize exposure.
mental animals, usually mice or rats (Fig.
37.3). The measure by inhalation is LC,,, or 37.2.3 SENSITIZATION
median lethal concentration. It is expressed as
an airborne concentration in milligrams of In some cases, an allergic reaction to a sub-
chemical per cubic meter (mg/m3) of air, or stance will develop with one exposure, or over
parts per million (ppm) in the air (Fig. 37.3). time with repeated exposures. This is called
sensitization. Once a person is sensitized to a
0 Oral and dermal routes:
substance, the extent of the reaction does not
necessarily relate to the degree of exposure.
Median lethal dose - LD, (mg/kg) Also, people who are sensitized to one chemi-
A large LD, (e.g., 5000 mglkg) equals a low degree cal may react to other similar materials. This is
of acute toxicity, typically relating to a low health known as cross sensitization (Fig. 37.4).
hazard. Certain individuals may be sensitized to some
chemicals used in the composites industry. For
0 Inhalation route: example, there have been reported cases of
Median lethal concentration - LC,, (rng/rn3)
epoxy sensitization. In these instances, it is
For rats, a four hour exposure period is commonly
important that an employee not be exposed
used. Because other time durations are used, data further, or allowed the opportunity to be
will usually be reported with time specified. exposed. To do this, engineering or adminis-
trative controls should be implemented. If
these are not possible or practical, then the
Fig. 37.3 Acute toxicity measures. employee should be removed from chemicals
causing reaction.
The acute inhalation hazard is dependent on
the material's toxicity, together with its physi-
cal properties, such as vapor pressure for gases 37.2.4 EXPOSURE LIMITS
or particle size for aerosols, particulates and
There are limits or values (Fig. 37.5) estab-
dusts. Knowledge of the physical properties
lished by health groups to assist the user in
will assist in determining whether a material is
controlling exposure to certain chemicals;
likely to become airborne, thus inhalable.
some are regulated (OSHA's Permissible
Chronic toxicity occurs when adverse health Exposure Limit, PEL), others are recom-
effects are manifested after exposure to a sub- mended (ACGIH's Threshold Limit Value,
stance over a long period of time (e.g. TLV). These limits are based on actual indus-
throughout a working lifetime) or by long-term trial experience, experimental animal and
effects resulting from one or a few doses. These human studies and, when possible, a combi-
effects can occur following repeated exposures nation of all three.
to chemical substances through dermal or ocu- Exposure limits are developed for protec-
lar contact, halation or ingestion routes. tion against serious health effects or irritation,
Chronic toxicity testing includes systemic narcosis, or nuisance. They are intended for
toxicity, mutagenicity carcinogenicity, repro- the control of potential health hazards in the
ductive toxicity and sometimes epidemiological workplace. Because each individual is differ-
studies, all of which are very time consuming ent, there will be incidents of people affected
 Industrial hygiene 825

Once sensitized (have an allergic reaction), the following may occur:

fl
0

0 .
9.

X
Low exposure
Low toxicity

fl0 9.

nw
X Extreme exposure = Allergic reaction
0 .

Low toxicity

Chemicals similar to
X = Allergic reaction
substance causing Low exposure
sensitization
Fig. 37.4 Sensitization equations.

by some substances at concentrations below 37.3 INDUSTRIAL HYGIENE

the PELs or TLVs (Fig. 37.5). This is because the Potential hazards can be controlled through the
limits/values are based on the exposed popu- implementation of sound industrial hygiene
lation being 'normal', and does not address practices. Whether employees are working in a
aggravation from pre-existing conditions, ill- high or low hazard area, the recognition, evalu-
nesses or lifestyle choices. It is best to maintain ation and control of conditions are necessary to
concentrations of atmospheric contaminants at avoid occupational illness or discomfort. This is
the lowest level reasonably possible through industrial hygiene.
process or engineering controls. It is important to apply good engineering,
When referencing PELs and TLVs, a 'skin' process and administrative controls in the work-
notation may be assigned. This indicates that place along with effective industrial hygiene
dermal exposure should also be considered practices (e.g. monitoring, surveys, proper per-
when evaluating exposure to that substance. sonal protective equipment usage). Without
Always check the current OSHA standards for addressing the fundamentals, it is difficult to
PELs and the latest edition of the ACGIHs maintain employee comfort and, hence, protec-
TLVs: Threshold Limit Values and Biological tion against exposures that may be present.
Exposure Indices, along with the supplier's Industrial hygiene practices for composites
Material Safety Data Sheet, for information on are common to those for other industries.
limits and protection against exposure.
826 Safety and health issues

Exposure limits
PEL (Permissible Exposure Limits) Airborne exposure limits issued by the OccupationalSafety and Health
Administration (OSHA), 29 CFR 1910.1000, which are legally binding.
TLV (Threshold Limit Values) Recommended exposure limits for airborne concentrations of substances.
They are issued by the American Conference of Governmental Industrial Hygienists (ACGIH) and pub-
lished annually.

Exposure limit descriptions

Both PEL and TLV are expressed in similar terms describing exposures:
TWA (Time Weighted Average) This represents a normal 8 h day and a 40 h work week, to which nearly all
workers may be exposed without adverse health effects. In literature, data will appear as PEL-TWA or
TLV-TWA.
STEL (Short-Term Exposure Limit) Concentrations to which people can be exposed for a short period of
time without suffering from
irritation;
0 chronic or irreversibletissue damage; or
0 narcosis of sufficient degree to increase likelihood of accidental injury, impairment of self-rescue or
reduction of work efficiency
provided the daily PEL or TLV-TWA is not exceeded.
Data will appear as PEL-STEL or TLV-STEL in written works.
C (Ceiling) The concentration not to be exceeded during any part of the working exposure. This will
appear as PEL-C or TLV-C in documentation.

Fig. 37.5 Exposure limit terminology.

Periodic exposure assessments should be con-
ducted taking into consideration routes of
exposure associated with composite use (Table
37.1). Monitoring should be routine, and on
demand whenever unusual odors are noticed,
visible contamination is heavier than normal,
or a new process is to be used. After any new
process or modification of an old one, good
work practice is to ensure that existing con-
trols to prevent exposure are implemented
and effective.
Two potential exposures posed by composite

Table 37.1 Routes of exposure for composite users

Skin and eyes Typically hands, lower arms and face are exposed. However, if personal hygiene is not
good, other areas of the body may be susceptible to exposure. Avoid exposure,
especially in cases where dermatitis or sensitization has been confirmed. Avoid contact
with chemicals that can be absorbed through the skin, as systemic and/or local
effects may occur.
Inhalation Good ventilation will minimize possible exposure from the release of solvents or dusts
generated.
Ingestion Thorough washing of the hands prior to eating or smoking provides sigmficant
protection from the effects of accidental ingestion.
Injection Needles and sharps are not normally a concern. However, shards from cured
composites or brittle fibers, or needles from weaving or sewing processes can
puncture the skin and chemicals could enter the body.
 Industrial hygiene 827

usage are skin contact with materials that
could result in irritation leading to dermatitis
or sensitization, and inhalation of particulates
from operations such as cutting, grinding and
finishing. Both concerns can be eliminated or
minimized with implementation of proper
gloves/clothing, good ventilation and process
conditions, and effective training.
37.3.1 ADMINISTRATIVE CONTROLS
In the National Safety Council’s Fundamentals
of Industrial Hygiene (3rd Edn), administrative
Table 37.2 Workplace tools to prevent exposures
controls are defined as ’methods of controlling
employee exposures by job rotation, work
assignment, or time periods away from the haz-
ard’. These controls may be implemented when
e n p e e r i n g controls cannot reduce the exposure
to permissible levels (Fig. 37.6). Administrative
controls also encompass ’other work rules’, such
as company policies (Table 37.2).
One example of a process hazard in the
composites industry, controllable through
engineering and administrative rules, is an
out-of-control exothermic reaction. This is an
unintentional runaway chemical reaction of a

1. Safety controls Confined space entry; hot work permits; lockout/tagout procedures; pipeline
breaking permits; safe work permits.
2. Personal controls Knowledge and use of Material Safety Data Sheets (MSDS);company policies
and procedures; regulation of employee’s exposure time in a work area.
3. Education and Training in the use and handling of materials and any associated hazards;
training understanding of the training.
4. Materials handling Information from MSDS on proper handling of materials
5. Process controls Isolation of process controlled work areas; eating, drinking, smoking should be
separate from any work area as should food storage; control of process-related
hazards, such as an out-of-control exothermic reaction potential. There should
be procedures, equipment, ventilation systems and process hazard analysis
and training in place; wet processes to reduce dust generation.
6. Personal hygiene Thorough washing of hands before each job break and eating/drinking/smoking
and toilet use along with use of good hand creams after each wash.
7. Warnings Proper labels on chemicals; follow OSHA’s Hazard Communication
and labels Standard.
8. Housekeeping Keep work areas clean and free of clutter; remove dust by vacuuming instead of
blowing it off work areas into the air.
9. Emergency plans Plans and procedures for dealing with any chemical emergency; personnel
should have the knowledge, skills and equipment to respond appropriately.
10. Ventilation General, diluted (supplied air) and local exhaust ventilation.
11. Medical controls Good occupational medical program and protocol.
12. Engineering Design, maintenance and hazard studies; shielding, monitoring devices, and
practices alarm systems.
13. Personal protective Respirators, gloves, body suits, boots, jackets, goggles, eyewear, face shields,
equipment safety shoes/boots, headgear.
14. Administrative Job rotation, scheduling machine times to reduce number of workers exposed,
controls scheduling work times to avoid exposures (eg. cooler times of day to avoid heat
stress), reduction of work periods.
828 Safety and health issues

I Engineering controls
I Exothermic reactions can be avoided and min-
imized by clearly defining and following the
J. proper procedures, thoroughly training
I-Administrativecontrols 1 employees who work with resins and prepreg
materials, making certain that equipment is in
1 good working order, and that safety devices or

Personal protective equipment (PPE) benzyl phthalate, ABP) are in place and func-

Fig. 37.6 Industrial hygiene order of priorities.

resin system, alone or in prepreg form, typi-
cally called an exotherm. It may occur under
any of these conditions:
0 heating or mixing a resin too long;
0 heating a resin too fast;
0 allowing a resin to get too hot;
0 contamination or mislabeled chemicals.
These factors have been known to start or
extend an exotherm:
0 resin mass scale up and equipment cannot
dissipate heat;
0 deviating from procedures;
0 disabling safety equipment;
0 casting hot melt resins too deep;
0 process equipment malfunction;
0 variability in raw materials;
0 mixing incompatible chemicals and curing
agents;
0 contaminating chemicals, e.g. poor house-
keeping;
0 uneven dispersing or mixing of chemicals;
0 trying to mass cure resin oE prepreg in an
oven or autoclave.
37.3.2 PERSONAL PROTECTIVE EQUIPMENT
(PPE)
Personal protective equipment is used to con-
trol exposures when they cannot be reduced to
an acceptable or practical level using engineer-
ing and administrative controls. In the
composite industry, there are three main expo-
sure areas that may require PPE to protect the
skin, eyes and lungs.
37.3.3 SKIN PROTECTION
Hand contact exposure is most common when
using composites. The use of proper protective
gloves is important to control exposure. Along
with gloves, other equipment such as jackets,
arm protectors, or body suits may be neces-
sary depending on the process or potential for
exposure.
Gloves
Glove selection should take into account the
parameters in Table 37.3 to ensure the correct

Table 37.3 Proper glove selection criteria

Chemical resistance Glove must be impermeable to the chemical being used. An incorrect glove
choice may allow the material to come in contact with the skin.
Dexterity and If the user cannot work comfortably with the glove, it will not be used.
comfort
Glove lining Lining material may cause irritation or excess sweating. Consider liners or other
alternatives.
Glove surface The outer surface may contain residual coatings that may contaminate and
possibly delaminate a composite part.
 lndustrial hygiene 829

glove choice and use by the employee. aramid protect well against heat, cuts or
Additionally, Table 37.4 gives a brief listing of scrapes. Glove choice must depend on the
glove types used in the composite industry job and its duration.
and what they protect against. SACMA's com-
panion video to the Save Your Skin! booklet
demonstrates correct glove selection and Skin creams
usage for composite users.
There are creams that are applied directly to
It is important to know that there is not an
the hands and forearms for protection. Two
'all purpose' glove for protection from all
types of cream discussed in Table 37.5 indicate
exposure. Proper protection may require
the difference between moisturizers (no pro-
wearing one type of glove over another.
tection against chemicals) and barrier creams
Basically, there are two glove types:
(limited protection). Barrier creams may be
1. Chemically resistant: used alone or in combination with gloves.
A selection of gloves used for protection When using barrier creams, there is a possi-
against exposure to chemicals. Depending bility of contamination to the composite
on the permeability of the glove material to material. If there is a heavy reliance on the use
the chemical used, the glove chosen will of barrier creams, process engineers need to
protect the wearer for only a limited time. investigate alternatives in engineering, process
Even the proper glove does not last forever. changes or alternate PPE. Since barrier creams
2. Mechanically or thermally resistant: are not moisturizing creams, a good moisturiz-
These gloves, such as leather, cotton or ing cream should also be applied after work to

Table 37.4 Examples of glove types

Glove type Hazard ...

Aramid Cutting, intense heat
Cotton Abrasions
Disposable plastic (Latex) Microorganisms, mild irritants, fibers
Natural rubber (Latex) Acetone (< 1 h), epoxies, methyl ethyl ketone (MEK), light work
Leather Abrasions, punctures, fibers
Metal mesh Cuts, scrapes
Neoprene Acetone (< 1 h), solid epoxies, DMSO, isopropyl alcohol
Nitrile Solid epoxies, TDI, isopropyl alcohol
Polyvinyl alcohol Methylene chloride, bisphenol A epoxies, toluene, MIBK, TDI,
styrene, THF (< 4 h), l,l,l-trichloroethane
Polyvinyl chloride TDI, isopropyl alcohol, (< 4 h)
Rubber, butyl Isopropyl alcohol, Dimethylformamide (DMF), DMSO. MEK, MIBK,
acetone, N-methyl-2-pyrrolidone (NMP)
Rubber, insulated Electrical shocks and burns
VITON@ Toluene, xylene, styrene, isopropyl alcohol, l,l,l-trichloroethane
Sources: Save Your Skin!, SACMA 1990; Safe Handling of Advanced Composite Materials, SACMA 1996.
830 Safety and health issues

Table 37.5 Skin creams

Moisturizing creams Replenish moisture in the skin which is lost after washing up. Use regularly to
avoid dry skin conditions which could lead to dermatitis. Gloves must always be
worn when moisturizing creams are used.
Barrier creams 1. Water repellent creams: Leave a thin film of lanolin, beeswax, petroleum or
silicone on skin. Used mainly in machine shop operations.
2. Solvent repellent creams: Leave a thin film on the skin, visible or not, which
will repel oils, paints, and solvents. Barrier creams do wear off and must be
reapplied for constant protection.

keep skin healthy. Additionally, barrier creams 37.4 POTENTIAL HEALTH AND SAFETY
may actually increase abrasion from fiber dust, HAZARDS IN COMPOSITE PROCESSES
so their effectiveness needs to be monitored. When designing equipment, processes and
modifications, complete containment of
37.3.4 EYE PROTECTION vapors and dusts should be a goal. General
ventilation should be provided to all work
Eye protection should be selected based on areas, with local exhaust equipment designed
impact (flying particles) and/or chemical to pull contaminants away from the
splash possibilities. Selections should include employee's breathing zone. In almost every
appropriate safety glasses, goggles, face composite process, the engineering emphasis
shields or a combination of these. is on good ventilation to control solvent and
dust exposures, along with other contami-
37.3.5 RESPIRATORY PROTECTION nants.
Figure 37.7 gives a summary of potential
During operations such as resin mixing, health and safety exposures that could occur
prepreg lay-up, machining or clean-up, respi- in composite processes. However, with good
ratory protection may be necessary to reduce engineering, administrative and industrial
exposures to vapors or dusts. hygiene practices, personal exposure can be
There are two main types of respirators: air minimized.
purifying and air supplying. Before using any Process improvements are driven by tech-
respirator, familiarity with OSHA's Respiratory nology and regulation (e.g. CA's South Coast
Protection Standard (29CFR 1910.134) is essen- Air Quality Management District Rules 1171
tial. Not everyone can or should use a and 1128 are for emission reduction of volatile
respirator. An employee must be medically organic compounds in coating and cleaning
approved, fit tested, and trained to assure that operations). In the composites industry, some
the respirator used is both appropriate and examples of minimized solvent vapors and
protective.
exposures include closed loop systems, cabin
If using a cartridge (filter) respirator, the surroundings for processes, improved ventila-
cartridges are specific to hazards and must be
tion designs and capture efficiencies, and
maintained and changed periodically to pre- elimination of solvents or substitution of low
vent exposure. If they are the wrong type, are vapor pressure solvents for high vapor pres-
used too long, or become dirty, respirators are
sure solvents.
ineffective.
 Toxicological properties of composite components 831

COMPOSITE PROCESSES

Fig. 37.7 Potential health and safety exposures in composite processes.

37.5 TOXICOLOGICALPROPERTIES OF effects, the resin system is of primary concern.

COMPOSITE COMPONENTS The reinforcement is secondary due to its lower
hazard potential compared to resin systems.
The supplier’s Material Safety Data Sheet
Solvents are addressed as a separate category as
(MSDS) and other sources of toxicological
they are major sources for potential skin and
information should be used for practical haz-
inhalation exposures. Some are part of the resin
ard assessment on any material. Rarely will
systems, while others are only used for clean-
data be available on the composite system
up purposes.
itself because the methodology has not been
fully developed to adequately test these kinds
of materials. Therefore, the hazards of com-
37.5.1 RESINS
posites are generally expressed in terms of the
components’ hazards. This is a conservative Composites are by definition based on a resin
approach that provides the user with the most system matrix applied to some reinforcing
protective information because it is based on material. The resin system is often quite com-
the most hazardous component which may plex, consisting of a basic resin (e.g. epoxy),
only be a percent or less of the entire mixture. which is formulated with other materials,
Typically, when discussing toxicological such as curing agents, diluents, accelerators,
832 Safety and health issues

pigments or solvents. Components of the
resin system may be supplied individually
and formulated by the user, supplied as ‘Part
A and Part B’ and blended before use, or sup-
plied mixed as a ’one-pack’ system.
any product containing additives with known
or potential health effects. Reference to the
MSDS will advise you of hazardous materials.
Some commonly used additives are listed in
Table 37.7.

Epoxy resins Other resin types

Epoxy resins, also known as glycidyl com- Over the years, epoxies have been the back-
pounds, are commonly used in composite bone of the composite industry. However,
matrix resin systems. In addition to the stan- other resin systems play an important role and
dard bisphenol A based epoxies, other are used for particular applications and perfor-
glycidyl ethers, glycidyl esters, glycidyl mance properties. Table 37.8 discusses health
amines, and epoxy novolacs are used in com- effects of some of these other resins. The asso-
posite matrices. ciated health hazards may appear severe, but
The greatest concern with epoxies is their exposures are avoidable through engineering
potential to cause skin irritation, dermatitis or and industrial hygiene practices, especially
skin sensitization, depending on the base good ventilation for control of vapors.
epoxy used and the sensitivity of the individ-
ual exposed. Table 37.6 discusses epoxy based 37.5.2 REINFORCING MATERIALS
resins and associated hazards.
Most reinforcement materials (Table 37.9) are
fibers, such as graphite or carbon, glass,
Hardenerskuring agentskatalysts
aramid or ceramic. Others may be used, but
One or more of these additives are used to the application is typically specialized, result-
enhance properties of composite materials. ing in small specialty runs. Overall, data
Their percentage of the resin system may be indicates that most fibers have a low hazard
small, but precautions ought to be taken for potential in initial form. However, they may

Table 37.6 Health effects of various epoxies

EPOXY type CAS nurnber(s) Known health efects Key notes

Bisphenol A based 1675-54-3, Possible skin sensitizer; Insufficient evidence to classify as
25036-25-3, low order of acute a carcinogen according to IARC.
25068-38-6, toxicity; slightly to Considering the many studies as
25098-99-8 moderately irritating. a whole, the evidence does not
show the resins to be carcinogenic.
Glycidyl amines 28768-32-3 Possible skin sensitizer; Mutagenicity tests gave both
low order of acute negative and positive results.
toxicity.
Cycloaliphatics 2336-87-0, Irritant to skin and mucous Not considered mutagenic or
30583-72-3 membranes. carcinogenic.
Glycidyl ethers 2210-79-9, Possible skin sensitizer. Neopentylglycol diglycidyl ether
2426-08-6, Moderate to severe skin has caused skin tumors when
3101-60-8, and mucous membrane applied repeatedly to skin of
17557-23-2, irritant. shaved mice.
26447-14-3
Toxicological properties of composite components 833
834 Safety and health issues
(.j
 Toxicological properties of composite components 835

Table 37.9 Health effects of fibers

Reinforcement type Known health effects Key notes

Carbon or graphite Mechanical abrasion and irritation
fibers of the skin; possible dermatitis;
physico-mechanical properties
of the fibers rather than a
toxico-chemical reaction. Possible
reaction from the fibersizing.
See resin health hazards.
Glass fibers Mechanical irritation
of eyes, nose, throat;
possible skin sensitization,
either from sizing or fiber.
Para-aramid fibers Minimal evidence for skin
irritation, none for skin
sensitization.Prolonged
overexposure to respirable
fibrous particles (RFP)
has potential for lasting
lung damage.
Ceramic fibers Skin, eye, or upper respiratory
irritation is possible.
PEL-TWA is 15 mg/m3 total dust, and PEL-
TWA of 5 mg/m3 for synthetic graphite
respirable dust. ACGIH has a TLV-TWA of
2 mg/m3 respirable dust for all forms of
graphite except fibers. There are no limits for
carbon fiber, though the US. Navy has set 3
carbon fibers/cc. EPA did not classify the
potential carcinogenic properties of
carbon fibers due to insufficient data.
Continuous fiber (used in composites, >6 km
in diameter) is probably not carcinogenic
(IARC, 1988).Wool fiber is classified as a
possible human carcinogen (IARCGroup 2B).
Commercial fibers are too large to inhale, but
RFP can be created when the fiber is abraded
or cut. Airborne RFP concentrations from
composite machining have been acceptably
low. Inhalation studies in rats demonstrated
fibrous particle breakdown in the lungs and
no carcinogenicity. IARC classifies para-
aramid RFP in Group I11 (not classified as a
carcinogen).
EPA proposed ceramic fibers, such as refrac-
tory aluminum oxide and zirconium oxide, as
not classifiable to human carcinogenicity.
Also, EPA proposed that aluminum silicate
fiber be classified as a human carcinogen.
Refractory ceramic fibers are classified
as 2B by IARC.

be chemically coated or stiff enough to cause
irritation by penetrating the skin or tissues of
the nose, throat or bronchi. Little has been
studied and is known about cured materials
being ground, drilled, milled, cut or sanded.
Should fragments of fibers be small enough to
be respirable, there is concern that a general or
fibrous dust hazard to the lungs can occur.
Therefore, precautions should be used to min-
imize exposure.
Knowledge of the fiber used should include:
length, diameter, aspect ratio and fragmenta-
tion propensity. Knowledge of fiber
parameters, along with how the composite will
be handled, is critical to protect from exposure.
Fiber diameter size for respirability is
believed to be 3.5 pm or less. Anything larger
than that will be removed from the body via
nose and throat functions. If the fibers are res-
pirable, the toxic effects may vary
significantly. There are low risk fibers (irritants
such as fiberglass) and there are significant
risk fibers that can result in asbestosis or can-
cer (such as asbestos fibers). Therefore, each
fiber should be assessed on its own toxicolog-
ical properties.
37.5.3 SOLVENTS
Solvents are used in many aspects of compos-
ites manufacturing, from resin formulation to
clean-up activities. There are several groups of
836 Safety and health issues

Table 37.10 Health effects of solvents

Solvents CAS Known health effects Key notes

nurnber(s)
Ketones Mild to moderate skin irritant; moderate to
severe eye irritant; if overexposure by
inhalation, possible central nervous system
(CNS) depression.
1. Acetone 67-64-1 Irritation of mucous membranes; headache,
2-propanone, DMK nausea. Skin contact can cause defatting,
dermatitis. Systemic effects only d e r repeated
overexposure. If ingested, vomiting may cause
acute chemical pneumonitis (lung damage).
2. Methyl ethyl 78-93-3 Few ill effects have been reported.
ketone, MEK Objectionable odor is reported. MEK has an
2-butanone odor threshold of 0.25-25 ppm. Eye, nose
and throat irritation at greater than 200 ppm.
3. Methyl isobutyl 108-10-1 Moderate to severe eye irritation; slight to PEL-TWA of 100 pprn and
ketone, MIBK moderate skin irritation; toxic by ingestion and TLV-TWA of 50 pprn and TLV.
dermal exposure; may cause CNS depression. STEL of 75 ppm.
Overexposure may cause kidney and liver effects.
Chlorinated solvents Exposure to high concentrations can cause cardi-
ovascular effects (sensitizationof the cardiac
muscle); CNS depression; chronic animal
exposures have caused liver and kidney changes.
1. Methylene chloride 75-09-2 Vapors below TLV levels; no adverse health
Dichloromethane responses expected; overexposures may cause
possible respiratory irritation due to vapors
which could lead to delayed pulmonary edema
and CNS depression. Liquid may cause skin
and eye irritation.
2. l,l,l-trichloroethane 71-55-6 Drowsiness; overexposures can cause CNS
Methyl chloroform depression which could lead to respiratory
arrest; animal studies indicate possible liver
and kidney damage.
Other solvents
1. Dimethylformamide, 68-12-2 Irritating to the skin, eyes and mucous
DMF membranes; stomach pain and cramps; nausea
and vomiting; DMF is readily absorbed through
the skin and may aid in absorption of other
materials; possible link to testicular cancer.
2.- N-Methylpymoli- 872-50-4 Severe dermatitis possible; irritating to skin,
done, NMP severe eye irritant; inhalation of high concen-
trations can cause headaches, giddiness, mental
confusion, nausea, gastric upset, and vomiting;
eye irritation.
PEL-TWA of 1000 pprn and TLV-
TWA of 500 ppm. ACGIH
indicates a TLV-STEL of 750 ppm.
PEL and TLV-TWA of 200 pprn
and TLV-STEL of 300 ppm. At the
TLV, workers complain of odor,
but few ill effects have been
reported.
TLV-TWA of 50 ppm, A2.PEL-
TWA at 25 ppm, PEL-STEL of
125 ppm. Possible human
carcinogen. IARC Group 28, NTP
Group 2.
PEL and TLV-TWA of 350 pprn
and TLV-STEL of 450 ppm.
MOSH has a recommended
exposure limit of 350 pprn as a
15 minute ceiling.
Possible human carcinogen (IARC,
Group 2B) PEL and TLV-TWA of
10 pprn (skin).A lethal single oral
dose of DMF for humans is
estimated to be 10 g.
Maximum airborne levels not
established. Manufacturers
suggest a TWA limit of
10-100 ppm (vapor), TWA of
5 mg/m3 (mist).

solvents, ketones and chlorinated, which have
dominated the industry. Known health effects
of major solvents are outlined in Table 37.10.
With increased concern for safety, health
and environmental impacts of solvents in the
workplace, the use of solvents is decreasing
and exposures are being minimized. When
choosing a solvent, make certain that regula-
tory investigation is done to avoid
unnecessary rework. It is possible that a sol-
vent of choice may become obsolete due to
emission regulations or toxicity concerns.
37.6 CONCLUSION
Every industry or business has hazards. The
maturity of the industry, its products, and his-
tory are all factors in what the hazards or risks
are and how they are controlled.
There are known potential health and safety
hazards in the composites industry, even
though it is a young technology compared to
mature ones such as steel. As the composites
industry develops, processes may change and
more specific health and safety issues may be
identified. Until then, each composite user has
the opportunity to implement the National
Safety Council’s ’engineering, education and
Although safe and healthful working conditions can be
justified on a cold dollars-and-cents basis, I prefer to
justify them on the basic principle that it is the right
thing to do. In discussing safety in industrial
operations, I have often heard it stated that the cost of
adequate health and safety measures would be
prohibitive and that ‘we can’t afford it.’
My answer to that is quite simple and quite direct. It is
this: ‘If we can’t afford safety, we can‘t afford to be in
business.’
Admiral Ben Moreell
President
Jones and Laughlin Steel Corp., 1948
Fig. 37.8 Safety philosophy (Laing and Schmidt,
1992). Used by permission of the National Safety
Council, Itasca, Illinois.
References 837
enforcement’ safety philosophy to control haz-
ards. This encompasses all the workplace tools
and techniques discussed.
Safety, encompassing health, should be
treated as a value. It is not a priority to be
raised or lowered with business cycles or man-
agement changes. It should be a constant
philosophy exhibited each day (Fig. 37.8). If it
is a value in the composites industry, then the
technology of composite materials can
develop naturally, without unnecessary hin-
drances impeding growth.
REFERENCES
American Conference of Governmental Industrial
Hygienists. 1997. 1997 TLVs@ and BEIS@,
Threshold Limit Valuesfor Chemical Substances and
Physical Agents, Biological Exposure Indices.
ACGIH.
International Agency for Research on Cancer, World
Health Organization. 1997. IARC Monographs on
the Evaluation of Carcinogenic Risks to Humans.
Vol. 68. IARC.
Laing, Schmidt. 1992.Accident Prevention Manual for
Business G. Industry, Administration G. Programs,
10th Edition. National Safety Council.
Laing, Schmidt. 1992.Accident Prevention Manual for
Business t3 Indust y, Engineering G. Technology,
10th Edition. National Safety Council.
OSHA Instruction CPL 2-2.20B CH-2. 1993. Polymer
Matrix Materials: Advanced Composites, Chapter
16. OSHA.
Plog, Benjamin, Kerwin, Schonfeld. 1988.
Fundamentals of Industrial Hygiene, Third
Edition. National Safety Council.
Suppliers of Advanced Composite Materials
Association. 1996. Safe Handling of Advanced
Composite Materials, Third Edition. SACMA.
Suppliers of Advanced Composite Materials
Association. 1990. Save Your Skin! A Guide to the
Prevention of Dermatitis. SACMA.
ACKNOWLEDGEMENT
Thanks and appreciation to the chemists,
industrial hygienists, toxicologists, and safety
professionals in the composite industry, par-
ticularly those in SACMA’s Environmental,
Safety, and Health Committee.