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Recent developments in the chemistry of

halogen-free flame retardant polymers

An overview of recent developments of the chemistry of halogen-free flame retardant
polymers is presented in this paper. The polymers or reactive monomers that are
inherently flamed retarding contain P, Si, B, N and other miscellaneous elements. They
can be used on their own or added to current bulk commercial polymers to enhance
flame retardancy. The synthetic chemistry of these molecules is discussed along with
their thermal stabilities and flame-retardant properties.

Thermal decomposition of polymer mixtures of PVC,

PET and ABS containing brominated flame retardant:
Formation of chlorinated and brominated organic

The thermal decomposition of various mixtures of acrylonitrile butadiene styrene

copolymer (ABS), ABS containing brominated epoxy resin flame retardant and Sb 2O3,
poly(ethylene terephthalate) (PET) and poly(vinyl chloride) (PVC) has been studied in
order to clarify the reactions between the components of mixed polymers. More than 40
halogen-containing molecules have been identified among the pyrolysis products of
mixed samples. Brominated and chlorinated aromatic esters were detected from the
mixtures containing PET and halogen-containing polymers. A series of chlorinated,
brominated and mixed chlorinated and brominated phenols and bisphenol A molecules
have been identified among the pyrolysis products of polymer mixtures containing flame
retarded ABS and PVC. It was established that the decomposition rate curves (DTG) of
the mixtures were not simple superpositions of the individual components indicating
interactions between the decomposition reactions of the polymer components. The
maximal rate of thermal decomposition of both ABS and PET decreases significantly if the
mixture contains brominated epoxy flame retardant and Sb 2O3 synergist. The
dehydrochlorination rate of PVC is enhanced in the presence of ABS or PET.

The ABS, PET, PVC and brominated epoxy flame retardant influence the decomposition
of each other. A series of brominated, chlorinated and both chlorinated and brominated
phenols and bisphenol A molecules forms if both PVC and brominated epoxy oligomer

flame retardant are present in the mixture. The PET decomposition radicals are ready
to stabilize with both Cl
or Br
radical in the presence of PVC or

brominated epoxy flame retardant. The brominated epoxy flame retardant and
Sb2O3 synergyst initiates the decomposition of ABS, this effect intensifies in the presence
of PET.

New Thinking on Flame Retardants

Kellyn S. Betts

No one wants their bed, couch, chair, computer, or TV to catch on fire. If an ordinary
upholstered chair in your home gets ignited, it can essentially take your whole house
down, says Richard Gann, a senior research scientist at the U.S. National Institute of
Standards and Technologys (NIST) Building and Fire Research Laboratory. The most
flammable part of a mattress or couch is its plastic polyurethane foam cushioning, he
explains. Once a fire gets through a chair or mattresss fabric covering and into this
cushioning, it can start a catastrophic reaction that quickly leads to flashover, in which
nearly everything combustible inside a room ignites simultaneously.
Until very recently, brominated flame retardants, especially polybrominated diphenyl
ethers (PBDEs), were one of the main materials used to reduce the speed with which the
plastic components of consumer goods including beds, couches, chairs, and electronics
could be consumed by fire. However, growing evidence shows that PBDE compounds are
escaping from the products they protect and making their way into the products users.
Moreover, the chemicals may disrupt human thyroid hormone functioning and cause
other health effects, prompting many nations to ban or suspend their use in new
consumer goods. [For more information on the health effects of PBDEs, see Unwelcome
Guest: PBDEs in Indoor Dust, p. A202 this issue.]
Although bromine- and chlorine-containing flame retardants are still used in some
products, the need for new alternatives is being driven by a confluence of policy,
standards, and pressure from environmental groups. Europe banned the use of two
formulations, PBDE pentaBDE and octaBDE, in 2004, the same year they were
withdrawn from the North American market. A third compound, decaBDE, was banned 1
April 2008 by the European Court of Justice. Stateside, Maine has banned the use of
decaBDE, the only PBDE still on the market in North America, in mattresses and
residential upholstered furniture produced and sold in that state, and will extend the ban
to electronics in 2010. Washington prohibits the use of decaBDE in mattresses and sets a
process for a future ban in furniture and electronics if the state can identify a safer and

feasible alternative that meets fire safety standards. Asian countries and other U.S. states
have similar legislation in the works.
Instead of adding new fire retardant chemicals that ultimately may be shown to cause
health problems, we should be asking whether we need to use these chemicals or if there
are other ways to achieve equivalent fire safety, contends Arlene Blum, a biophysical
chemist and visiting scholar at the University of California, Berkeley. So many of the
chemicals we have banned in the past were flame retardantsthink about asbestos,
polychlorinated biphenyls, polybrominated biphenyls, tris(2,3-dibromopropyl)
phosphate, PBDEs[and] they all ended up in the environment and in people, she
points out. We need to think carefully about adding these sorts of chemicals to
consumer products before there is adequate health information.
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Policy Drivers
Two new standards from the U.S. Consumer Product Safety Commission (CPSC) are
opening the door for innovative approaches for protecting consumer goods containing
polyurethane foam from fire. The first took effect last year for mattresses. This standard
is innovative in being the first in the United States to focus on the rate of heat release,
which fire safety experts recognize is the main determinant of how quickly a fire can
spread out of control to the flashover point, Gann says.
The mattress industry worked with NIST to develop the new standard test method to
meet the CPSC regulation, which stipulates that no mattress may generate a peak heat
release rate greater than 200 kilowatts when subjected to gas burners that mimic
burning bedding. The CPSC estimates the new standard will prevent as many as 270 firerelated deaths and 1,330 injuries every year. Since this is a performance standard rather
than a prescribed mattress design, it allows manufacturers to choose how to fabricate
mattresses that comply with the regulation, Gann says.
One approach mattress manufacturers are using to meet the standard is to employ what
is known in the industry as a barrier material, says Tom Ohlemiller, who was the project
leader for the NIST team that developed the mattress test method. The barrier materials
themselves may be inherently nonflammable, such as polyamides like Kevlar.
Flammable barriers may be protected with proprietary fire retardant treatments such as
decaBDE. However, Ohlemiller says the standard does not require such treatments for
the polyurethane foam padding beneath the barrier, which some scientists believe is the
source of some of the PBDE flame retardants that have escaped into peoples homes.
Over the past year, scientists have reported detecting other flame retardants used in
polyurethane foam in household dust.
The second new standard, which affects upholstered furniture, is still wending its way
through the regulatory process. According to Nancy Nord, acting chairman of the CPSC,

the new rule will address upholstered furniture fires without requiring the use of fire
retardant chemicals. Under the new proposal, furniture manufacturers could meet the
performance standard by using smolder-resistant cover fabrics or interior fire-resistant
barriers to protect the furnitures internal filling material. The standard was put out for
public comment in the Federal Register on 4 March 2008 and is open for comment until
May 19.
The furniture standard focuses on cigarettes as a source of fires because they are
responsible for 90% of the fires involving upholstery, says Russell Batson, vice president
of government affairs for the American Home Furnishings Alliance, an industry group.
You can get smolder resistance without relying on chemicals, he says. However, Gann
points out that cigarette ignition resistance is going to be improved significantly
anyway due to the passage over the past four years of laws mandating that Canada and
24 U.S. states can sell only fire-safe cigarettes, which self-extinguish if left unattended.
These laws affect nearly 60% of the North American population, according to the
nonprofit Coalition for Fire-Safe Cigarettes.
Additionally, Alexander Morgan, a group leader at the University of Dayton Research
Institute, says there is a lot of concern about barriers failing against ignition sources
stronger than a cigarette, especially since smoking rates are declining in many developed
nations, according to the World Health Organization. He says candles, hot electrical
equipment, and short-circuiting laptops could easily penetrate these protective barriers.
This is a fundamental weakness of the barrier approach in light of several decades of fire
safety data for furniture from the United Kingdom, which Morgan says has the worlds
toughest flammability standards for polyurethane foam. Yes, they do use flame
retardants, but the level of fire safety of their products is very good and fire losses in the
UK due to furniture fires are quite low or non-existent. When and if flashover occurs due
to a furniture fire, the amount of pollution and carcinogens released from this one fire
far overwhelms the production of potentially dangerous products from a flame retardant
foam, he says. Morgan argues that the solution may be to devise flame retardants that
are less likely to escape from the materials that they protect, together with better product
reclamation and recycling programs for flame retardant products so that the chemicals
dont end up into the environment.
Despite such concerns, Batson says the proposed standard is inspiring furniture
manufacturers to investigate how barriers can be used to insulate the interior cushioning
materials inside upholstered furniture. Recent innovations in materials science,
together with concerns about flame retardant toxicity and ecotoxicity have convinced
people in the industry to try to design effective barrier materials for the market, he says.
The furniture industry is looking carefully at how mattress manufacturers construct fireblocking barrier layers of fabric or high-loft materials such as batting rather than
chemically loading the outer fabric layer, he says. That approach and some of the

technologies that are emerging in response to it is probably going to be useful in the

furniture [industry], as well, he says.
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One promising approach is to incorporate flame retardants into the materials
themselves. A new company called G3 Technology Innovations (G3i) is pursuing that
line of reasoning with its GreenShield FR treatment for polyester fabrics. Such fabrics
are the basis of 90% of the products used in the contract textile industrywhich
produces all furniture, floor coverings, wall coverings, and window treatments used in
commercial buildings and institutionssays Alex Qiao, G3i s co-founder and president.
The technology, which G3i co-founder and chief operating officer Suresh Sunderrajan
and his business partners developed for different applications while previously employed
at Eastman Kodak, revolves around the ability to attach different functional groups onto
nanoparticles. We are able to attach multiple sets of these [functional molecules] onto
the particles, he explains. For example, he says one set of the molecules might
encompass the particles needed to allow the molecules to attach themselves to a fabrics
fibers, a second set might provide water and stain repellency, and a third set could
involve flame retardancy. All of this is built onto a [silica-based] backbone which is
inherently nonflammable, he explains. The GreenShield FR treatment goes into the
[polyester] fiber and becomes a permanent part of it, Qiao says.
The company has also worked with a textile finisher called Preferred Finishing to
develop new barrier materials that Qiao says can become integral parts of the fabric they
protect because both are made of polyester resin. This confers an additional advantage of
avoiding the use of melamineformaldehyde resin, which is often used to bind other
barriers to decorative fabrics, Sunderrajan points out. When the resin degrades, he
explains, it releases formaldehyde, which the International Agency for Research on
Cancer classifies as a known human carcinogen. The company says all of its technologies
are based upon commercially available materials that have been tested individually for
toxicity. Several furniture makers are now testing the G3i products.
Nanoclays are another material that could change the way consumer products are
protected from combustion. Flame retardants made with naturally occurring clay called
montmorillonite are poised to have a huge influence on future fire safety, Gann says.
Scientists at NIST and Cornell University have been investigating how this clay can help
reduce the amount of energy released during fires for more than a decade, says Jeffrey
Gilman, a research chemist at NIST.
When things burn, contrary to how it looks, it is not the solid that is burning. The solid
breaks down to give you small fragments of molecules. These vaporize and mix with the
air, and they burn there, Gann explains. The nano-network formed by the nanoclays

impedes this from happening, he says. If the [nanoclay] particles are appropriately
spread out and dispersed through the host [material], they form sort of a gauze inside
the material. It slows down significantly or even prevents the breakdown of material and
the release of gas-phase combustible molecules, he says.
The potential of nanoclays isnt just theoretical. A company called Nanocor sells
nanoclay-based flame retardants that are used in electronics, wires, cables, and
decorative wallpapers, says Tie Lan, general manager for the companys U.S. operations.
The fundamental nature of the nanoclay will make the material burn slower [and] lower
the temperature of the flame, he says, adding that the same clays are also used in
nonclumping kitty litters.
Both Nanocor and Albemarle Corporation, one of the major flame retardant makers, sell
flame retardants combining nanoclays with another major class of flame retardants
based on metal hydroxides. The nanoclays synergistically improve how the metal
hydroxide retardants perform, Gilman says. Combining the two flame retardants also
improves how the plastics are processed, as well as their material properties. Nanoclays
are appealing to plastics manufacturers because they can be added in relatively small
amounts, on the order of a few percent by weight. This means both that they are unlikely
to negatively affect the functionality of the plastic material to which they are added and
that they are relatively inexpensive, Gann says.
More recently, the NIST researchers have also begun to look at other nanomaterials,
including carbon nanotubes, layered hydroxides, and polyhedral oligomeric
silsesquioxane nanocomposites that also contain silicon, says Gilman. Some
nanomaterials, especially carbon nanofibers, appear to have promise for use in
polyurethane foam, says Mauro Zammarano, a guest researcher from Italy evaluating
these materials at NIST. Testing at NIST suggests carbon nanofibers are able to reduce
the rate at which heat is released when polyurethane foam is burned.
However, Andrew Maynard, chief science advisor of the Project on Emerging
Nanotechnologies, a nonprofit group associated with the Woodrow Wilson International
Center for Scholars, cautions that the same properties that make the nanoparticles
effective could also make them toxic. With any sort of nanotechnology . . . [the]
potential for harm is associated with the size and shape of the particles, as well as what
theyre made of. That applies whether youre looking at sunscreen, impregnated fabrics,
or flame retardants, he says. Scientists need to look carefully to determine if there is any
way the nanomaterial-based flame retardants escape from the fabric or material in which
theyre used and enter the environment, and whether people could be exposed to the
nanoparticles, he says.
NIST has begun to work with the CPSC and Scripps Institution of Oceanography to
evaluate whether any of these nanomaterial-based fire retardants are toxic, Gilman says.
Dimitri Deheyn, a marine biologist at Scripps Marine Biology Division, is conducting

some of this testing using brittle stars, which Deheyn says have nervous systems that
function very similarly to mammals, including humans. He says the testing he has
conducted to date suggests the surfactants used to ensure the nanomaterials disperse
throughout the materials to which they are added may be more toxic than the
nanomaterials themselves.
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Halogen-Free Electronics
The electronics industry is under pressure from environmental groups to remove
potentially toxic compounds from their products, including the brominated flame
retardants that were once widely used in electronics housings and cases and are still used
extensively in printed circuit boards. At least nine leading electronics companies have
pledged to remove brominated and/or halogenated flame retardants from some or all of
their products, according to the Environmental Working Group.
The main way that companies are doing this is by using phosphorus-based flame
retardants for casings and circuit boards, and using minerals such as nanoclays in
combination with aluminum and magnesium hydroxide for the machinerys wiring and
cabling, says Morgan. However, he points out that companies and environmental
watchdogs are scrutinizing some of these phosphorus-based retardants for potential
health problems of their own; for example, some are suspected to be neurotoxicants
when they break down in the environment, he points out. He says his experience testing
how well different nonhalogenated flame retardants work suggests that reactive
phosphorus-based retardants appear to be the best nonhalogenated flame retardants for
printed circuit boards at this time, in terms of their effectiveness, long-term durability,
sustainability, and environmental impact.
Trying to find halogen-free alternatives for electronic circuit boards involves significant
trade-offs, stresses Fern Abrams, the director of government relations and
environmental policy for IPC, an electronics industry association for manufacturers of
printed circuit boards and other electronics components. She says the holy grail would
be to develop materials for building and housing electronics that are inherently flameresistant.
Morgan agrees. He says the aerospace industry currently uses some inherently nonflammable plastics, but they are too expensive for commodity-type applications such as
electronics housings, given the industrys profit margins. More recently, scientists have
begun trying to develop plastic polymers that are inherently nontoxic and
One team involved in this effort is at the University of Massachusetts Amherst, where
researchers have developed a new plastic polymer based on bishydroxydeoxybenzoin
(BHDB) that releases water vapor rather than hazardous gases when it breaks down in a

fire. The great thing about BHDB is that . . . it is extremely fire-safe and does not
contain halogenated additives, says Bryan Coughlin of the universitys Polymer Science
and Engineering Department, one of the new materials co-inventors.
The Amherst researchers believe BHDB may prove to be cost-effective for use in some
consumer products, including home furnishings and electronics. We are currently
trying to determine how well BHDB works in a variety of plastics formulations . . .
including polyurethane foam, says Todd Emrick, another co-inventor at the University
of Massachusetts Amherst Polymer Science and Engineering Department. The fire safety
experts at NIST say that they believe the material has a great deal of promise. But the
biggest challenge, as Morgan points out, may be finding a company willing to make the
investment needed to bring such an innovative technology to the marketplace.

Although house dust is known to be a predominant source of exposure to PBDEs, its not
yet clear which part of the dust these chemicals bind to. The dust pictured above
contains pet hair (rust brown), pollen (yellow), plant fibers (green), dead ...
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Suggested Reading

Kashiwagi T. Flame retardant mechanism of the nanotubes-based

nanocomposites. Gaithersburg, MD: National Institute of Standards and
Technology; 2007. Final report. NIST GCR 07-912.

Morgan AB, Wilkie CA, editors. Flame retardant polymer

nanocomposites. Hoboken, NJ: John Wiley & Sons; 2007.

Nelson GL, Wilkie CA, editors. ACS Symposium Series #797. Washington, DC:
American Chemical Society; 2001. Fire and polymers: materials solutions for
hazard prevention.

U.S. EPA. Washington, DC: U.S. Environmental Protection Agency; 2005.

Environmental profiles of chemical flame-retardant alternatives for low-density
polyurethane foam, volume 2: chemical hazard reviews. EPA 742-R-05-002B.

Overview of Flame Retardants Including

Magnesium Hydroxide
Matthew D. Walter

Mark T. Wajer
8140 Corporate Drive, Suite 220
Baltimore, MD 21236
There are many classes of compounds which are useful as flame retardants.
minerals, organo-phosphates, and halogenated compounds are all commonly
used for
their ability to inhibit combustion and smoke generation in plastics and other
materials. In
1993, United States industries consumed 810 million pounds of flame retardant
additives, and demand is projected to be over one billion pounds in 19981
. While
currently a small part of this large market, Magnesium Hydroxide is attracting
because of its performance, price, low corrosiveness, and low toxicity. The
market for magnesium hydroxide in flame retardants is about ten million pounds
year, with the potential to surpass thirty million pounds per year in the near
Basic Fundamentals of Various Flame Retardants
ATH, Magnesium Hydroxide
Like ATH* (Al2O33H2O), magnesium hydroxide (Mg(OH)2), is an acid- and
halogenfree flame retardant for various plastics. Both hydroxides decompose
when heated according to the reactions:
2Al(OH)3 ---> Al2O3 + 3H2O
Mg(OH)2 ---> MgO + H2O
The gaseous water phase is believed to envelop the flame, thereby excluding
and diluting flammable gases.2

Similar to the function of char formed by phosphorouscontaining flame

retardants, a heat insulating material may form on the surface of the
plastic in contact with the flame, reducing the flow of potentially flammable
decomposition products to the gas phase where combustion occurs." In both of
reactions, the decomposition products are non-toxic and the mineral phases,
MgO, are alkaline, reducing the likelihood of acidic, corrosive gases exiting the
The physical and chemical properties of magnesium hydroxide and ATH are
shown in
Table One. Magnesium hydroxide has a 100C higher decomposition temperature
ATH, allowing a higher processing temperature in compounding and extruding
plastic. Also, magnesium hydroxide adsorbs more energy during the
process.Table One: Comparison of Properties of Mg(OH)2 and ATH
Bound Water, % 31.0 34.6
Specific Gravity 2.36 2.42
Mohs Hardness 2.5 3.0
Refractive Index 1.56 - 1.58 1.57
Initial Decomposition Temperature 330C 230C
Enthalpy of Decomposition 328 cal/g 280 cal/g
Table One: Comparison of Properties of Mg(OH) and ATH.
Phosphorous-Containing Flame Retardants
Phosphorous-containing flame retardants mainly influence name retardancy in
condensed phase. They are particularly effective in materials having a high
content, such as cellulose and some oxygen-containing plastics. The basic flame

retarding mechanism involves thermal conversion of the phosphorous-containing

retardant to phosphoric acid in the condensed phase of the plastic. The
phosphoric acid
extracts water from the burning plastic, causing it to char. The char insulates the
from flame and heat, preventing volatile, combustible gases from exiting the
phosphoric acid is formed in the burning plastic, there is increased likelihood that
smoke will be corrosive. Halogenated organophosphates are sometimes used as
a flame
The halogens, as will be shown in the next section, interfere with the radical
chain reaction, while the phosphorous forms a char.
Halogenated Flame Retardants
Halogenated name retardants are organo-halides selected to vaporize in a
temperature range as that of the plastic resin. Once in the gas phase, the
typically chlorine or bromine, decreases the concentration of high energy free
that are involved in the combustion process.3
Eliminating these free radicals reduces
flame intensity, decreases the amount of heat transferred to the plastic,
slowing or eliminating the burning of the plastic. A mechanism for this action has
proposed as follows:3
In the gas phase, a radical chain reaction occurs involving OH and H radicals
formed by
high energy decomposition of the plastic:

+ O2 ---> OH.
+ O..
.. + H2 ---> OH.
+ H.
To remove these high-energy free radicals, the halogenated flame retardant first
down as shown:
RX ---> R.
+ X. where X is either Cl or Br.
The halogen radical reacts to form the hydrogen halide:
+ RH ---> R.
+ HX
which in turn interferes with the radical chain mechanism:
HX + OH.
---> H2O + X.
The high energy H.
and OH.
radicals involved in combustion of the plastic are thus removed by the flame
retardant and replaced with lower energy X.
radicals. These
radicals react with the plastic hydrocarbons to produce the hydrogen halide,
the flame retardant.
Since halogenated flame retardants are regenerative, much lower loadings

~10% by weight) are required compared to ATH or magnesium hydroxide

~50% by weight). Brominated flame retardants are typically more effective than
utilizing chlorine because of a narrower vaporization temperature leading to
concentration of the flame retardant in the flame zone.3
Synergistic agents, such as
antimony oxides, further increase the effectiveness of both brominated and
flame retardants by enabling the halogen to stay in the flame zone for longer
While halogenated flame retardants and halogen-antimony combinations provide
name retardance in most systems, use of these compounds has given rise to
concern.5,6 In particular, much attention has been focused on the corrosiveness
toxicity of smoke and other emission products generated during the combustion
plastics utilizing these materials. In recent years there has been much
speculation that
legislation will arise restricting the use of these compounds as flame retardants.
brominated flame retardant producers have voluntarily agreed to put restrictions
production, export, and import of their products in European countries in
advance of such
In contrast to the potentially hazardous halogenated flame retardants,
magnesium hydroxide is considered a nuisance dust and is not volatilized during
combustion of the plastic. Table Two shows toxicity data for brominated and

Additionally, as landfill space declines, or becomes unpopular, incineration and

of used plastics will become more widespread. Plastics formulated with
flame retardants pose problems for incinerators in design, operation and
as well as a danger to public health from the incineration product gases.8
Table Two: Range of Toxicity Values for Flame Retardant Types
Compound Class Toxicity, LD50 Reference
Brominated, (inhalation) 2.49-200 mg/L 9
Chlorinated, (inhalation) 2.25-203 mg/L 10
Magnesium Hydroxide, (inhalation) None published, Mg(OH), is
considered a nuisance dust 11
Table Two: Toxicity Values for Flame Retardant Types
Use of Magnesium Hydroxide as a Flame Retardant in Plastics
There are many producers of magnesium hydroxide for flame retardants.12
Marietta Magnesia Specialties, LLC, the Solem Division of J.M. Huber, and Morton
International are the larger domestic producers with Dead Sea Periclase (Israel),
(Japan), and Magnifin (Austria) being some of the foreign producers. Grades of
magnesium hydroxide range from coated, micronized powders (for higher end,
loading applications) to uncoated magnesium hydroxide as a direct replacement
for ATH.
Kyowa and Magnifin specialize in the more expensive coated, high-end grades of
magnesium hydroxide while Martin Marietta Magnesia Specialties, LLC produces
MagShieldTM S in uncoated form as a direct ATH replacement.
Several studies13,14,15,16 illustrating the effectiveness of magnesium
hydroxide as a flame

retardant in plastics have been performed. These have concluded that

hydroxide is effective at reducing smoke emissions from burning plastics. A
summary of
the more important factors determining the performance of magnesium
hydroxide as a
flame retardant follow:1. The endothermic decomposition commencing at about
330C for magnesium
hydroxide (versus about 230C for ATH) withdraws heat from the substrate,
slowing the rate of thermal degradation of the plastic.
2. The release of water vapor upon decomposition of magnesium hydroxide
the fuel supply present in the gas phase.
3. The relatively high heat capacities of both magnesium hydroxide and the
decomposition products formed upon decomposition of magnesium hydroxide
reduce the thermal energy available to degrade the plastic.
4. The decomposition products provide increased insulation of the plastic from
heat source through char formation.
5. The high filler content usually associated with magnesium hydroxide-treated
plastics acts as a solid phase dilutent.
Figure 117 shows typical results of smoke emission testing (ASTM E662, under
conditions) on various plastics with and without 40% by weight of magnesium
The magnesium hydroxide in this study significantly lowers the overall level of
produced. Furthermore, the use of magnesium hydroxide causes a considerable
delay in
the onset of smoke evolution and markedly slows the rate of smoke release.
these factors have major implications in real life.

Another study18 showed the results of UL 94 testing (Ignitability of Plastics by a

Flame, or Vertical Burn Test) where polyamide and polypropylene plastics were
compounded with Mg(OH)2 at 60% by weight loading. These compositions
attained a
VO classification representing a high resistance to ignition, according to the UL
94 test.
For a flame retardant to be useful in compounded plastics, it must not degrade
physical properties of the plastic. In a typical flexible wire PVC formulation,
Marietta Magnesia Specialties LLC's MagShieldTM S was found to slightly improve
physical properties of the PVC formulation compared to ATH and a competing,
grade magnesium hydroxide. The compounded PVC utilized a 30 PHR loading of
flame retardant and resulted in a plastic with the properties19 shown in Table
Three.Table Three: Physical Properties of a Typical Flexible Wire and Cable PVC
Formulation with Magnesium Hydroxide and ATH
MagShieldTM S ATH Competitive
Elongation, % 139 118 136
Tensile Breaking Strength, psi 2610 2365 2499
Tensile Modulus, psi 20330 19173 20116
Melt Flow Index, (g/10 min) 0.90 0.43 1.00
Table Three: Data from Martin Marietta Magnesia Specialties LLC testing
Plastics requiring higher loadings, such as polypropylene and polyamides,
require the use of specialty magnesium hydroxide grades having fatty acid
coatings or
specific physical properties. The special properties of these materials allow for

loadings with little to no degradation of the physical properties of the plastic.

New work
underway with metallocene catalyzed polymers indicates that coating of the
hydroxide may be reduced or eliminated for various plastics.20
Magnesium hydroxide acts as a flame retardant and smoke suppresser in plastics
by withdrawing heat from the plastic during its decomposition into magnesium
oxide and
water. The water vapor that is generated dilutes the fuel supply to the flame.
Decomposition products insulate the plastic from heat and produce char that
the flow of potentially flammable gases to the flame.
Increasing legislation and concern about the use and recyclability of halogenated
retardants make magnesium hydroxide more attractive to plastics producers.
hydroxide offers flame retardance and smoke suppression from a substance that
is acidand halogen-free and has low toxicity values. In most cases, with proper
selection of the
grade of magnesium hydroxide, no compromise need be made for physical
properties and name retardancy of the plastic. For high-loading applications
where the use of highend or coated magnesium hydroxide is dictated, legislation
maybe the dominant driving
force for specifying magnesium hydroxide as opposed to halogenated flame
The more economical route for lower loading applications may be the use of
grades of magnesium hydroxides such as MagShield TM S.
*Also known as aluminum hydroxide, Al(OH)3
1. HAIRSTON, D.W., Chemical Engineering, 9 (1995), 65.
2. HORNSBY, P.R. and WATSON, C.L., Polymer Degradation and Stability, 30
(990), 74.

Course Work Materials in New Developments and Future Trends in Europe and
the United States for Fire Retardant Polymer Products, (1989).
4. HASTIE, J.W., High Temperature Vapors, Academic Press, LLC, New York,
1975, p. 353.
5. WOOLEY, W.D. and FARDELL, P.J., Fire Safety Journal, 5 (1982), 29-48.
6. REINKE, R.E. and REINHARDT, C.F., Modem Plastics, 50 (1983), 94-98.
7. From Industrial Minerals, 336 (1995), 17.
8. GANN, R.G., from Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed.,
Volume 10, 935.
9. Material Safety Data Sheets from Ethyl Corporation for
and dibromoneopentylglycol.
10. Material Safety Data Sheets from Velsicol Chemical Company for chlorendic
anhydride and Occidental Chemical Corporation for
11. Sax's Dangerous Properties of lndustrial Materials, 8th Edition, R.J. Lewis, Sr.,
Vol. 111 (992), 2150.
12. From Industrial Minerals, 318 (1994), 23-45.
13. ZIEGAN, G. and HONGESBERG, H., from Flame Retardants '92, 5th
Conference, 120-132.
14. HORNSBY, P.R., Fire and Materials, 18 (5), (1994), 269-276.
15. LEVESQUE, J.L. and HASTBAKA, M.A., from RETEC Additive Approaches to
Polymer Modification Conference Papers, (9/1989), R89-190.
16. HORNSBY, P.R. and WATSON, C.L., Polymer Degradation and Stability, 30
(990) 73-87.
17. From Reference 14, p. 272.18. From Reference 14, p. 275.
19. Taken from MagShieldTM 98 Product Literature, Martin Marietta Magnesia
Specialties, LLC

20. HUGGARD, M., Flame Retardant Polyolefins: Impact and Flow Enhancement
Using Metallocene Polymers, Conference Proceedings (Additives for
Metallocene Catalyzed Polymers, June 24-26, 1996), Intertech Conferences,
411 U.S. Route One, Portland, MA 04105, p. 9.
NOTICE The data and test results referred to herein are based on tests defined by
flammability safety regulations
and performed under laboratory conditions. This should not be construed as a
representation or warranty of
performance under actual fire conditions. The information contained herein is, to
the best of our knowledge and
belief, accurate. Any recommendations or suggestions made are without
warranty or guarantee of results since
conditions of use are beyond our control. Before using, the customer should
determine the suitability of the product
for the customer's intended application. We warrant only that this product will
meet the specifications set forth herein.
MERCHANTABILITY. Our only obligation is to replace nonconforming product or to
refund purchase price at our
option. In no event shall we be liable in tort, contract or otherwise for any
incidental or consequential damages.
MagShield is a trademark of
Martin Marietta Magnesia Specialties LLC

Use of flame retardant polymer grades on the rise in electric/electronic & building industries

Plastics materials are used in large volumes in major applications such as buildings, vehicles and electronic appliances. In each of these
areas fire safety is critical. Fire is a big menace. As per estimates from USA, there are approximately 400,000 residential fires each year,
20% involving electrical distribution and appliances; another 10% concerning upholstered furniture and mattresses. These fires kill about
4,000 people, injure another 20,000 people and result in property losses amounting to about US$4.5 bln. The use of flame retardant
plastics can reduce deaths by 20%. Flame retardants can act in a variety of ways: by raising the ignition temperature, reducing the rate of
burning, reducing flame spread and reducing smoke generation. Hence flame retardants have been developed to improve the properties
of plastics under the different conditions of processing and use. Flame retardants are an important part of fire protection as they not only
reduce the risk of a fire starting, but also the risk of the fire spreading. The increasing demands in the electrical and electronic sector for
miniaturisation and faster injection moulding cycles exerts additional demand on flame retardant technology. The faster injection speeds
require higher processing temperature stability and increased flow performance; while miniaturisation leads to increasing property
performance for a given resin system as less material is used in each part. Flame retardants in commodity polymers are growing
exceptionally well since the inherent flame retardant polymers are relatively more expensive. Environmental, health and technical
concerns and regulations like REACH, RoHS, WEEE will change the market of flame retardants along with other additives used in
In all, over 175 different types of FRs exist, commonly divided into four major groups: inorganic FRs, organophosphorus FRs, nitrogencontaining FRs and halogenated organic FRs.
Inorganic FRs comprise metal hydroxides (e.g. aluminium hydroxide and magnesium hydroxide), ammonium polyphosphate, boron salts,
inorganic antimony, tin, zinc and molybdenum compounds, as well as elemental red phosphorous. Inorganic FRs are added as fillers into
the polymers and are considered immobile, in contrast to the organic additive FRs. Organophosphorous FRs are primarily phosphate
esters that may also contain bromine or chlorine. Organophosphorous FRs are widely used both in polymers and textile cellulose fibers.
Nitrogen-containing FRs inhibit the formation of flammable gases and are primarily used in polymers containing nitrogen, such as
polyurethane and polyamide. The most important nitrogen-based FRs is melamine and melamine derivatives.
The main flame retardant systems currently in use are polymeric based brominated solutions which have a range of performance
characteristics offering a choice of solutions depending on specific critical performance requirements. Brominated additives will continue
to lead the flame retardant additive market in total value. Phosphorus-based flame retardants will grow at the fastest pace, driven by
increasing trends towards non-halogenated products. Rapid gains are also expected in inorganic flame retardants such as aluminum
hydroxide and magnesium hydroxide which are finding more use in polyolefins. Halogen-free and phosphorous-free route is the most
difficult, and also the most environment friendly, with a limited choice of FR additives. The newer technologies being developed include
flame retardants combining nanoclays with another major class of flame retardants based on metal hydroxides. The nanoclays
synergistically improve how the metal hydroxide retardants perform, improve how the plastics are processed, as well as their material
properties. Nanoclays are appealing to use because they can be added in relatively small amounts. Some nanomaterials, especially
carbon nanofibers, appear to have promise for use in polyurethane foam.
Flame retardants can interfere, inhibit or even suppress the combustion process during a particular stage of the fire: heating,
decomposition, ignition or flame spread. There are two types of action, chemical or physical. Generally chemical actions are more
efficient than physical ones. The chemical actions can be:
Reaction in the gas phase: The radical gas phase combustion process is interrupted by the flame retardant, resulting in cooling the
system, reducing and eventually suppressing the flammable gas flux.
Reaction in the solid phase: The flame retardant builds up a char layer protecting the polymer against oxygen and heat.
The physical actions can be:
Cooling: Endothermic processes cool the polymer to a temperature inhibiting the fire.
Formation of a solid or gaseous protective layer against heat and oxygen needed to sustain the combustion.
Dilution effects: Inert fillers reduce the combustible carbon content, and additives releasing inert gases dilute the fuel in the solid and
gaseous phases.
Organic and inorganic phosphorous compounds have a good fire safety performance and are fast developing to meet halogen free
requirements. Nitrogen-containing flame retardants are of lower efficiency and are combined with phosphorous compounds to boost their
efficiency. Inorganic compounds, particularly aluminum and magnesium hydroxides, must be used at high levels to compensate for their
lower efficiency and meet high fire safety performances. HFFR polymers with increasing oxygen index values are Polysulfones, PEEK,
Liquid crystal polymers (LCP), Melamines (MF), Polyamides (PI), Polyamide-imide (PAI), Polyetherimide (PEI), Polyphenylenesulfide
(PPS), Polybenzimidazole (PBI).

US demand for flame retardants will rise 3.8% pa to 1 bln lbs in 2013, reflecting more stringent fire codes and flammability requirements,
especially in building materials and consumer products, as per Freedonia. Additionally, an improved economic outlook in key applications,
such as wire and cable insulation and jacketing, and motor vehicles, will fuel demand. Nonetheless, overall gains will be limited by cost
sensitivity in price-competitive markets such as motor vehicles and textiles, as well as environmental and health concerns over several
flame retardant chemicals. In value terms, flame retardant demand will advance nearly 4% pa to US$1.1 bln in 2013. This represents a
deceleration from the 2003-2008 period, which was characterized by rapid price increases for flame retardants as a result of high raw
material and energy costs. Phosphorus-based flame retardants will grow at the fastest pace, driven by increasing trends toward nonhalogenated products. However, brominated compounds will continue to lead the market in total value, as the regulatory climate in the US
is unlikely to undergo dramatic changes in the near future. Rapid gains are also expected for smaller-volume flame retardants, such as
magnesium hydroxide, which is finding increased use in polypropylene and engineering resins. Alumina trihydrate (ATH) will remain the
largest volume flame retardant through 2013, comprising 46% of demand and growing slightly faster than the overall market

Flame retardants are chemicals used in thermoplastics, thermosets, textiles and coatings that inhibit or
resist the spread of fire. These can be separated into several different classes of chemicals:


Minerals such as aluminium hydroxide ATH, magnesium hydroxide MDH, huntite and hydromagnesite,[1][2][3][4]
various hydrates, red phosphorus, and boron compounds, mostly borates.

Organohalogen Compounds. These include organochlorines such as, chlorendic acid derivatives
and chlorinated paraffins; organobromines such as decabromodiphenyl ether (decaBDE), decabromodiphenyl ethane (a
replacement for decaBDE), polymeric brominated compounds such as brominated polystyrenes, brominated carbonate
oligomers (BCOs), brominated epoxy oligomers (BEOs), tetrabromophthalic anyhydride, tetrabromobisphenol A (TBBPA)
and hexabromocyclododecane (HBCD). Most but not all halogenated flame retardants are used in conjunction with a
synergist to enhance their efficiency. Antimony trioxide is widely used but other forms of antimony such as the
pentoxide and sodium antimonate are also used.
Organophosphorus compounds such as organophosphates, tris(2,3-dibromopropyl) phosphate, TPP, RDP,
BPADP, tri-o-cresyl phosphate, phosphonates such as DMMP and phosphinates. There is also an important class of flame
retardants that contain both phosphorus and halogen, examples of such are the chlorophosphates like TMCP and TDCP.

Mineral flame retardants are typically additive while organohalogen and organophosphorus can be either
reactive or additive. The basic mechanisms of flame retardancy vary depending on the specific flame
retardant and the substrate. Additive and reactive flame-retardant chemicals can function in the vapor or
condensed phase.
The annual consumption of flame retardants is currently over 1.5 million tonnes per year, which is the
equivalent of a sales volume of approx. 1.9 billion Euro (2.4 billion US-$).[6]
1 Mechanisms of function
1.1 Endothermic degradation
1.2 Thermal shielding
1.3 Dilution of gas phase
1.4 Gas phase radical quenching

2 Environmental prevalence
2.1 Health concerns
2.2 Sudden infant death syndrome
3 See also
4 References
5 External links
Mechanisms of function
Endothermic degradation
Some compounds break down endothermically when subjected to high temperatures. Magnesium and
aluminium hydroxides are an example, together with various carbonates and hydrates such as mixtures
of huntite and hydromagnesite.[1][4][5] The reaction removes heat from the substrate, thereby cooling the
material. The use of hydroxides and hydrates is limited by their relatively low decomposition temperature,
which limits the maximum processing temperature of the polymers (typically used in polyolefins for wire
and cable applications).
Thermal shielding
A way to stop spreading of the flame over the material is to create a thermal insulation barrier between the
burning and unburned parts. Intumescent additives are often employed; their role is to turn the polymer
into a char, which separates the flame from the material and slows the heat transfer to the unburned fuel.
Dilution of gas phase
Inert gases (most often carbon dioxide and water) produced by thermal degradation of some materials act
as diluents of the combustible gases, lowering their partial pressures and the partial pressure of oxygen,
and slowing the reaction rate.[3][5]
Gas phase radical quenching
Chlorinated and brominated materials undergo thermal degradation and release hydrogen
chloride and hydrogen bromide or if used in the presence of a synergist like antimony trioxide antimony
halides. These react with the highly reactive H and OH radicals in the flame, resulting in an inactive
molecule and a Cl or Br radical. The halogen radical has much lower energy than H or OH, and therefore
has much lower potential to propagate the radical oxidation reactions of combustion.
As of 2008 the United States, Europe and Asia have a annual consumption rate for flame retardants at 1.8
million metric tons and valued at $4.20-4.25 billion dollars. According to the Ceresana Research, the market
for flame retardants is increasing due to rising safety standards worldwide and the increase use of flame
retardants. It is forecasted that the global flame retardant market will generate $5.8 billion dollars (US). As
of 2010, the Asia-Pacific region was the largest market for flame retardants which was approximately 41%
of global demand followed by North America, and Western Europe.
Environmental prevalence

In 2009, the U.S. National Oceanic and Atmospheric Administration (NOAA) released a report on
polybrominated diphenyl ethers (PBDEs) and found that, in contrast to earlier reports, they were found
throughout the U.S. coastal zone.[7] This nationwide survey found that New Yorks Hudson Raritan Estuary
had the highest overall concentrations of PBDEs, both in sediments and shellfish. Individual sites with the
highest PBDE measurements were found in shellfish taken from Anaheim Bay, California, and four sites in
the Hudson Raritan Estuary. Watersheds that include the Southern California Bight, Puget Sound, the
central and eastern Gulf of Mexico off the Tampa-St. Petersburg, Fla. coast, and Lake Michigan waters near
Chicago and Gary, Ind. also were found to have high PBDE concentrations.
Health concerns
Brominated flame retardants have faced renewed attention in recent years. The earliest flame
retardants, polychlorinated biphenyls (PCBs) were banned in 1977 when it was discovered that they are
toxic.[8] Industries shifted to using brominated flame retardants instead, but these are now receiving closer
scrutiny. The EU has banned several types of polybrominated diphenyl ethers (PBDEs) as of 2008, 10 years
after Sweden discovered that they were accumulating in breast milk.[9] As of December 2009, negotiations
between EPA and the two U.S. producers of DecaBDE (a flame retardant that has been used in electronics,
wire and cable insulation, textiles, automobiles and airplanes, and other applications), Albemarle
Corporation and Chemtura Corporation, and the largest U.S. importer, ICL Industrial Products, Inc., resulted
in commitments by these companies to phase out decaBDE for most uses in the United States by December
31, 2012, and to end all uses by the end of 2013.[10] The state of California has listed the flame retardant
chemical chlorinated Tris (tris(1,3-dichloro-2-propyl) phosphate or TDCPP) as a chemical known to cause
cancer. In December 2012, the California nonprofit Center for Environmental Health filed notices of intent to
sue several leading retailers and producers of baby products for violating California law for failing to label
products containing this cancer-causing flame retardant. The demand for brominated and chlorinated flame
retardants in North America and Western Europe is declining, it is rising in all other regions.[6]
Nearly all Americans tested have trace levels of flame retardants in their body. Recent research links some
of this exposure to dust on television sets, which may have been generated from the heating of the flame
retardants in the TV. Careless disposal of TVs and other appliances such as microwaves or old computers
may greatly increase the amount of environmental contamination.[11] A recent study conducted by Harley et
al. 2010[12] on pregnant women, living in a low-income, predominantly Mexican-immigrant community in
California showed a significant decrease in fecundity associated with PBDE exposure in women.
Another study conducted by Chevrier et al. 2010[13] measured the concentration of 10 PBDE congeners, free
thyroxine (T4), total T4, and thyroid-stimulating hormone (TSH) in 270 pregnant women around the 27th
week of gestation. Associations between PBDEs and free and total T4 were found to be statistically
insignificant. However, authors did find a significant association amongst exposure to PBDEs and lower TSH
during pregnancy, which may have implications for maternal health and fetal development.
A prospective, longitudinal cohort study initiated after 11 September 2001, including 329 mothers who
delivered in one of three hospitals in lower Manhattan, New York, was conducted by Herbstman et al. 2010.
Authors of this study analyzed 210 cord blood specimens for selected PBDE congeners and assessed
neurodevelopmental effects in the children at 1248 and 72 months of age. Results showed that children
who had higher cord blood concentrations of polybrominated diphenyl ethers (PBDEs) scored lower on tests
of mental and motor development at 14 and 6 years of age. This was the first study to report any such
associations in humans.
A similar study was conducted by Roze et al. 2009[15] in Netherlands on 62 mothers and children to estimate
associations between 12 Organohalogen compounds (OHCs), including polychlorinated biphenyls (PCBs) and
brominated diphenyl ether (PBDE) flame retardants, measured in maternal serum during the 35th week of
pregnancy and motor performance (coordination, fine motor skills), cognition (intelligence, visual
perception, visuomotor integration, inhibitory control, verbal memory, and attention), and behavior scores
at 56 years of age. Authors demonstrated for the first time that transplacental transfer of polybrominated

flame retardants was associated with the development of children at school age.
Another interesting study was conducted by Rose et al. 2010[16] to measure circulating PBDE levels in 100
children between 2 to 5 years of age from California. The PBDE levels according to this study, in 2- to 5year-old California children was 10 to 1,000 fold higher than European children, 5 times higher than other
U.S. children and 2 to 10 times higher than U.S. adults. They also found that diet, indoor environment, and
social factors influenced childrens body burden levels. Eating poultry and pork contributed to elevated body
burdens for nearly all types of flame retardants. Study also found that lower maternal education was
independently and significantly associated with higher levels of most flame retardant congeners in the
San Antonio Statement on Brominated and Chlorinated Flame Retardants 2010:[17] A group of 145
prominent scientists from 22 countries signed the first-ever consensus statement documenting health
hazards from flame retardant chemicals found at high levels in home furniture, electronics, insulation, and
other products. This statement documents that, with limited fire safety benefit, these flame retardants can
cause serious health issues, and, as types of flame retardants are banned, the alternatives should be
proven safe before being used. The group also wants to change widespread policies that require use of
flame retardants.
A number of recent studies suggest that dietary intake is one of the main routes to human exposure to
PBDEs. In recent years, PBDEs have become widespread environmental pollutants, while body burden in the
general population has been increasing. The results do show notable coincidences between the China,
Europe, Japan, and United States such as dairy products, fish, and seafood being a cause of human
exposure to PBDEs due to the environmental pollutant.
A February 2012 study genetically engineered female mice to have mutations in the x-chromosome MECP2
gene, linked to Rett Syndrome, a disorder in humans similar to autism. After exposure to BDE-47 (a PDBE)
their offspring, who were also exposed, had lower birth weights and survivability and showed sociability and
learning deficits.
A January 2013 study of mice showed brain damage from BDP-49, via inhibiting of the mitochdrial ATP
production process necessary for brain cells to get energy. Toxicity was at very low levels. The study offers
a possible pathway by which PDBEs lead to
This checklist is cited from the Department of Health in Washington state.
Cleaning - PBDEs in indoor dust is one of the primary sources of people's exposure. Reduce your exposure to
indoor dust. Use a damp cloth to dust indoor living and working areas. Avoid stirring the dust into the air. Use a vacuum
with a HEPA filter. Open windows and doors while you clean. Wash hands after dusting and cleaning.
Foam products - New foam items that you purchase today are unlikely to contain PBDEs. [citation needed] However,
mattresses, mattress pads, couches, easy chairs, foam pillows, carpet padding, and other foam products purchased
before 2005 likely contain PBDEs. Replace older foam products that have ripped covers or foam that is misshapen or
breaking down. If you can't replace the item, try to keep the covers intact. When removing old carpet foam, keep the
work area sealed from other areas of the house, avoid breathing in the dust, and use a HEPA-filter vacuum for cleanup.
Electronics - Deca-BDE has been used in electronics for years but is now being phased out of most electronics.
When purchasing electronics, request products that contain no Deca-BDE or other bromine-containing fire retardants.
Foods - PBDEs can concentrate in the fat of poultry, red meat, fish and other fatty meats. See how to reduce
the fat when preparing and cooking fish (these tips can be applied to other meats). Wash hands before preparing and
eating food.
Disposal and recycling - PBDEs will continue to pollute the environment unless flame retardant products are

disposed of properly. To keep PBDEs out of the environment, dispose of foam containing products and electronics such
as TVs and computers at your nearest hazardous waste collection site.

Sudden infant death syndrome

Main article: Sudden infant death syndrome#Toxic_gases

UK scientist Barry Richardson claimed in 1989 that a fungus in bedding broke down the antimony,
phosphorus, and arsenic flame retardants in infant bedding to form toxic gases. This research was taken up
by New Zealand scientist Jim Sprott, who published a book on the topic, and eventually aired on The Cook
Report in 1994. A 1998 UK government-sponsored study called the Limerick Report found that toxic gases
were not created.[18] Based on the Limerick report, position papers publicized by US SIDS
organizations[19] say there is not enough evidence to support the toxic gas theory, and that parents should
continue to put their babies to sleep on vinyl-covered crib mattresses. However, Sprott maintains that his
findings were not refuted

Read more:

Over the past few years, the use of certain types of halogenated flame retardant additives such as
decabromodiphenylether has come under intense scrutiny due to their toxicity, environmental persistence and
bio-accumulation. There is an immediate need for the development of non-toxic alternative flame retardant
materials and fire resistant polymers with comparable or better efficacies, obtained using benign synthetic
approaches. Enzymatic polymerization is being used increasingly as an environmentally friendly alternative
method for the synthesis of functional materials including polymers and additives. Here, we report a biocatalytic
synthesis of a new class of thermally stable, ultra-fire resistant polyphenols based on deoxybenzoins. In
calorimetric studies, these polyphenols exhibit very low heat release capacities (comparable to Nomex) and
form a large amount of carbonaceous char rendering them suitable for flame retardant applications.

Huntite is a carbonate mineral with the chemical formula Mg3Ca(CO3)4


3.4 Nitrogen-based flame retardants

Melamine is a thermally stable crystalline product characterized by a
melting point as high as 345 C that contains 67 wt% nitrogen atoms [23].

Melamine sublimates at about 350 C. Upon sublimati on, a significant

amount of energy is absorbed, decreasing the temperature. At high
temperature, melamine decomposes with the elimination of ammonia, which
dilutes oxygen and combustible gases and leads to the formation of thermally
stable condensates, known as melam, melem and melon (Fig. 15) [63].
These reactions compete with melamine volatilization and are more
pronounced if melamine volatilization is impeded, e.g. by the formation of a
protective layer. The formation of melam, melem and melon generates
residues in the condensed phase and results in endothermal processes, also
effective for flame retardancy. In addition, melamine can form thermally
stable salts with strong acids: melamine cyanurate, melamine phosphate,
and melamine pyrophosphate. Melamine and melamine salts are
characterized by various flame retardant mechanisms. Upon heating,
melamine-based salts dissociate and the re-formed melamine volatilizes, like
neat melamine, but a large proportion of the melamine undergoes more
progressive condensation than in the case of pure melamine [63]. The action
of salts in the condensed phase is therefore significantly higher.
The thermal decomposition of melamine phosphate (Fig. 16) leads to
the formation of melamine polyphosphate, with the release of melamine and
phosphoric acid [43]. The phosphoric acid released is known to
phosphorylate many polymers and produce flame retardant effects similar to
phosphorus-based flame retardant additives.

How Flame Retardants Are Used in Transportation

A wide variety of plastics, textiles and composite materials are used extensively in the
mechanical, structural and decorative parts of todays transport, including airplanes, trains and
cars. These materials are: (i) highly adaptable to new designs; (ii) lighter weight, making them
more energy efficient; (iii) less labor intensive; and (iv) more cost effective. Flame retardants are
often used to ensure these materials can meet flammability standards.
To make materials fire-resistant, flame retardants act to help stop or slow the spread of fire. They
can be used alone, or in combination with other flame retardants that act as synergists to
enhance fire retardant properties. If a fire does start, flame retardant solutions work in different
ways to help stop or minimize its effects. Learn more about how flame retardants work.
Different classes of flame retardants work to reduce the threat of fire hazards in different ways,
and must be matched to the specific material being used and the performance specifications of
the final product. There is no one-size-fits-all solution when essential fire-protection benefits must
be balanced with ensuring optimal performance.
Today, travel is safer than ever before, regardless of the mode of transportation. Thousands of
people take to the highways, railways and air daily, and they do so with the expectation of
reaching their destinations safely. Flame retardants play an important role in helping to meet that
expectation of safety.

The August 2005 fiery crash of a passenger jet in Toronto, Canada, in which all 309 people
aboard survived, is a prime example of how flame retardants can contribute to passenger safety.
Safety officials considered the fire-retardant material now required in airplane cabins to be a
factor in slowing the spread of the fire and allowing passengers to escape safely.
As the transportation industry evolves, and more emphasis is put on the production of lighter
weight, more fuel-efficient modes of transportation, technologically advanced materials will
increasingly be used, and fire protection will remain a public safety priority. NAFRA members will
continue to innovate and develop new and sustainable flame retardant solutions to keep pace
with advances in transportation and public safety standards.

Electrical & Electronic Equipment Key Role of Flame Retardants


Key Role of Flame Retardants

Plastic components are a part of almost all of todays electrical and electronic equipment
(EEE). The characteristics of plastic (i.e. versatile, flexible, and easy to mold into complicated
shapes and small sizes) make it the material of choice for EEE. But, this material also must meet
important fire safety standards. Miniature components in high-powered computers, for example,
generate a high concentration of heat sources that can lead to rapid overheating of internal
components. Electrical and electronic products are also subject to fire risks from electrical short
circuits that can cause ignition within a product, or external ignition sources such as candles
close to heat-generating equipment. Without the use of flame retardants to help protect materials
and components against fire, the potential for fire dangers increases as the number of electronic
productsand the cables, wires and electronic chargers to power themincreases in
households, offices and commercial buildings.
Incorporating flame retardants into the materials used in electrical and electronic components
lets manufacturers meet fire safety standards, while also ensuring a product meets key technical
requirements, including weight, durability, flexibility and performance specifications. Flame
retardants provide specific and critical fire protection properties. They increase a products
resistance to both internal and external heat sources that, potentially, could turn into sources of
fires. They also provide EEE with fire resistance characteristics so that internal electrical and
electronic components do not fuel a fire that has started outside of the equipment.
As new and more sophisticated material technologies emerge, and requirements for fire resistant
materials evolve, the flame retardant industry must keep pace. Flame retardant manufacturers
will continue to innovate and develop effective and sustainable flame retardants that meet new
product demands for fire resistance, high performance and cost-effectiveness, and address
environmental health and safety concern

There are no U.S. federal standards regulating upholstered furnishings. However, the
Consumer Products Safety Commission (CSPC) is in the process of drafting federal safety
standards for these products.
In 1975, with the implementation of Technical Bulletin 117 (TB 117), California became the
first state to set some flammability requirements for upholstered furniture paddings, and it is
still the only state with fire safety regulations for upholstered furniture. Californias TB 117
requires upholstered furniture paddings to withstand 12 seconds of an open flame without
spreading the flame.
In the United States, fire codes set by the International Fire Code and the National Fire
Protection Association (NFPA), and the NFPAs Life Safety Code require that upholstered
furniture in health care facilities and university and college dormitories without building
sprinkler systems, and all detention facilities must meet the requirements of California
Technical Bulletin 133. This standard requires upholstered furniture to meet certain
thresholds for heat release. Those same locations are required by these codes to comply with
a test for cigarette smoldering.
For residential upholstered furniture, manufacturers, who are members of the Upholstered
Furniture Action Council (UFAC), voluntarily comply with the UFAC smoldering test, which
tests upholsterys resistance to ignition from smoldering cigarettes.
Mattresses used in homes, including youth and crib mattresses, must meet two federal
flammability standards set by the CPSC. The first, 16 CFR 1633, is a test that measures heat
release when mattresses are exposed to an open flame. The second, 16 CFR 1632, tests
mattress components to ignition from smoldering cigarettes and it applies to all mattresses.
In 1988, the UK enacted the Furniture and Furnishings (Fire) (Safety) Regulations, a strict set
of regulations requiring all upholstery fabrics and polyurethane foams used in upholstered
furniture (domestic and commercial) to meet fire tests. In 1989, the requirements were
extended to other filling materials and in 1993 to mattresses. The regulation set flammability
requirements based on both smoldering (cigarette) and flaming ignition tests. Fabrics had to
meet a match ignition test while foams had to meet a test with a larger ignition source: a
wood crib. The tests required no ignition or very low flame spread.
A December 2009 report, commissioned in the U.K. by the Consumer and Competition
Policy Directorate of the Department for Business, Innovation and Skills (BIS), examined the
effectiveness of that nations flammability standards for furniture and furnishings. An
analysis of fire data offered a strong endorsement of the regulations and the use of flame
retardants they require. The report found: Both the number and lethality of F&F (furniture
and furnishings regulations) fires rose before the introduction of the regulations and fell
afterwards. According to BIS, the reduction in the rate and lethality of F&F fires was
estimated to equate to 54 lives saved per year, 780 fewer casualties per year and 1065 fewer

fires per year in the period 2003-2007. Learn more about the protective benefits of flame

From residential homes to commercial buildings, and from hospitals to schools, architects and
designers rely on plastics to help maximize energy efficiency, durability and performance. In
addition to potentially lightening a structures environmental footprint, properly installed plastic
building products can help reduce energy and maintenance costs over many years. In todays
cars and trucks, a key driver in boosting fuel efficiency, reducing emissions and lowering costs
for motorists is plastic. And in the kitchen plastic packaging helps keep food fresh and safe until
were ready to use it. Plastics have a proven track record of helping to save livesbut not before
they are rigorously evaluated for safety.
In automotive design, plastics have contributed to a multitude of innovations in safety,
performance and fuel efficiency. Todays plastics make up 50 percent of the volume of new cars
but only 10 percent of the weight, which helps make cars lighter and more fuel efficient, resulting
in fewer CO2 emissions. Tough, modern plastics also help improve passenger safety and auto
designers rely on the versatility of plastics when designing todays cool cars.
Food Safety
Plastics play an important role delivering a safe, healthy and abundant food supply that families
rely on everyday. In the store, clear plastic overwrap protects food while allowing consumers to
see through the packaging. In the home, sealable plastic bags, wraps and containers can
contribute to a longer, fresher shelf life for perishable foods.
Child Safety
At every turn, plastics are there to help parents protect their children. Moldable plastics allow
safer, rounded corners on everything from toys to high chairs and car seats. Plastics strength,
light weight and shape-shifting versatility also contribute to child-resistant medicine bottles, easyto-install safety latches and gates, and many other handy devices to help keep little explorers out
of trouble.
Sports Safety
Sports are a great way to keep active and stay healthy, but they can also lead to injuries.
Fortunately, innovations in plastics have helped to make essential safety geartems like plastic
helmets, mouth guards, goggles and protective paddinglighter and stronger to help keep
sports enthusiasts of all ages safe. Molded, shock-absorbent plastic foam helps keep feet stable
and supported, while the rugged plastics shells covering helmets and pads help protect heads,
joints and bones.

Plastics Myth BustersHeard Something About Plastics? Get the Facts Here
Determining fact from fiction on the Internet can be harder than you think. We know because
people often contact us with questions about rumors concerning plastics. And since many of
these might sound scientific or seem like good common sense, it's only natural to be concerned.
Visit this site if you've heard a rumor about plastics and want to know more.
Bisphenol-A (BPA)/Polycarbonate
A comprehensive resource for environmental, health and safety information about bisphenol A
(BPA), an industrial chemical used primarily to make polycarbonate plastic and epoxy resins.

Flame retardants are an important component in reducing the devastating impact of fires on
people, property and the environment. Their areas of application in electrical and electronic
equipment (EEE) vary depending on the materials being used, the function of the product,
and the level of fire resistance that must be achieved based on fire safety standards. Flame
retardants have unique characteristics, and, as a result, need to be matched appropriately to
the materials used.
In wires and cables, for example, the flame retardants used must meet fire safety
requirements developed specifically for these products because they have the potential for
spreading a fire to the electrical socket, and to walls and curtains. The level of flame
retardancy required for printed wiring boards used in consumer mobile phones is different
than that of wiring boards used in computer servers or in telecommunications or aerospace
applications. Higher electrical and mechanical performance demands must be met with flame
retardants that can achieve higher flammability and fire resistance standards, without
affecting a products performance specifications.
When it comes to fire safety, one size does not fit all. Specific flame retardants must be
selected carefully to meet fire safety standards, electrical and mechanical requirements.
The following classes of flame retardants used in EEE include:

Bromine-based flame retardants, predominantly TBBPA (help prevent fires

from starting or slow down a fire)
Chlorine-based flame retardants (work to stop flame formation)
Nitrogen-based flame retardants (stop the decomposition process and
prevent the release of flammable gases)
Phosphorus-based flame retardants (promote charring and prevent the
release of flammable gases; provide a barrier between the material and heat
Metal hydroxide and oxide flame retardants (slow down the decomposition
process and the release of flammable gases; can be used alone or as synergists
to boost other flame retardants benefits
Combinations of flame retardants are also used for maximum efficiency in
specific material applications

Find out more about the classes of flame retardants.

Flame retarding requirementsand the choice of flame retardant solutionswill vary with
the properties of the materials used for each specific product and the level and type of
mechanical and electrical functions the product must perform.

Environmental contaminants are a serious concern for many marine species. The main environmental toxins that
are currently a concern for populations of marine mammals are known as persistent organic pollutants (POPs)
and include PCBs, PBDEs and dioxins and furans. Many of these human produced chemicals are
bioaccumulated, meaning that organisms absorb these chemicals at a rate faster than they are lost. Predatory
animals acquire the lifetime accumulation of POPs of the animals they eat. This leads to biomagnification,
whereby the concentration of POPs increases greatly at every step in the food chain, and top predators, such as
killer whales, end up with extremely high levels.
The chemicals:
Polychlorinated biphenyls (PCBs)
Polychlorinated biphenyls (PCBs) were first introduced into the environment in the early 1900s where they were
used in a variety of adhesives, sealants, paints, hydraulic fluids, coolants and electric transformer insulating
fluids. PCBs were banned in Canada and the US in the 1970s but persist in the environment. They are still
produced and used in some parts of the world.
According to Dr Peter Ross at the Institute of Ocean Sciences, PCBs are considered of highest concern to
marine life. PCBs have been associated with toxic effects in marine mammals such as endocrine disruption,
which can cause impairment of reproduction, development, and other hormonally mediated processes, and
immunotoxicity, giving rise to an increased susceptibility to infectious diseases and cancers.
Polybrominated diphenyl ethers (PBDE)
PBDEs are a relatively new class of flame retardants that have been added to a variety of plastic products,
including fabrics, furniture, and especially electronics such as computers. PBDEs are present in increasing
concentrations in the environment and are still produced and used in North America. PBDEs are chemically

similar to PCBs and the metabolites of PBDEs (the chemical that forms when the body attempts to break down
PBDEs) are likely to interfere with hormones, uptake of Vitamin A, neurological development and the immune
Dioxins and Furans
Dioxins and furans are closely related chemicals that are produced when organic material is burned in the
presence of chlorine. Common sources include coal-fired generators, municipal waste incinerators, metal
smelting, pulp and paper mills, diesel engines, sewage sludge, and the burning of preservative-treated wood and
trash. Dioxins and furans persist in the marine environment and are extremely toxic in minute amounts the
most toxic dioxin is ten times more toxic than the most toxic PCB.
POPs and Cetaceans
POPs are stored in the fat of animals that consume them, which makes marine mammals particularly vulnerable
as contaminants will accumulate in their thick layer of blubber. Endocrine system disruption and immunotoxicity
are the two serious issues that arise from POP exposure, and these toxins are difficult to metabolize and
eliminate in long-lived species such as killer whales. In fact, recent studies have shown that killer whales of the
Pacific Northwest are some of the most contaminated marine mammals in the world. Killer whales are top
predators in the oceans food chain and therefore receive high contaminant loads from their prey. Research by
Dr. Peter Ross has shown that Biggs killer whales (transients), being mammal predators, feed highest up the
food chain and therefore have the highest level of POPs.
Where the animals forage may also affect the contaminant load they receive. For example, the difference in
northern and southern resident killer whales POP accumulation is significantly different. While both populations
have the same preference for chinook salmon, the southern residents killer whales, who spend the summer
months around the Puget Sound area of Washington and in the southern Strait of Georgia in British Columbia,
have accumulated toxin levels four times higher than the northern resident population, found along the central
and northern coasts of British Columbia during the summer and fall. Cullon et al found that the cause of this
discrepancy is the Chinook that these populations eat. The salmon consumed by southern resident killer whales
is exposed to higher toxin levels in more urbanized areas. Southern residents also need to eat more of this
contaminated prey, as Chinook nearing the end of their migrations in the south are less fatty.
POPs are not only acquired by consuming contaminant-laden prey, but are also passed from female to calf
during gestation and nursing. They are mainly transferred via the rich, fatty milk produced by the mother. A
females first calf receives the largest contaminant load compared to the load received by subsequent calves.
While this transfer of contaminants from female to calf may be very harmful for the calf, it does mean that
females reduce their contaminant load significantly every time they rear young. This release of toxins through
lactation means that the POP load of adult females is roughly 30% less than that of adult males.
The Arctic is a region that appears seemingly untouched by modern human existence, but sadly this is not the
case. POPs from all over the world arrive in the Arctic via atmospheric and ocean circulation. The result is that
animals at the top of the food chain, such as belugas, narwhals and polar bears, accumulate tremendous
amounts of contaminants the way killer whales and other marine mammals do in more southern latitudes, closer
to direct pollution sources. Research by Desforges et al. attests to the issue of Arctic pollution and female POP
offload to offspring, although in this case it was via transplacental transfer and not lactation. This study found that
female belugas transferred 11.4% of their PCBs and 11.1% of their PBDE blubber burden to their fetuses in
Oil Spills
Oil spills are also a major threat to marine life and cetaceans do not appear to avoid areas affected by oil. They
have little if any sense of smell and are unable to detect oil vapour in the air. While they do have excellent eye
sight, they dont appear to recognize surface oil as a hazard. Oil vapour is very toxic and causes respiratory
distress when inhaled. Whales are also in danger if they eat oiled prey. Biggs killer whales (transients) can
consume oil adhering to the bodies and fur of their mammalian meals, and ingestion of oil can cause serious
long-term damage to internal organs. Baleen whales are also particularly vulnerable to oil while feeding, as oil
may stick to their baleen while they filter feed near oil slicks.

The 1989 Exxon Valdez disaster in Alaska sadly illustrated the damaging effects of oil on killer whale groups.
One resident pod (AB) was photographed in an oil slick shortly after the spill and suffered the loss of 33% of its
members within a year. Its rate of reproduction has been lower than average ever since, and the pod fractured
following the death of a matriarch. Members of the AT1 transient population were also photographed in oil from
the Exxon Valdez, and 41% of its members were lost in the following year. There has been zero reproduction in
this group since the spill and this genetically distinct transient population is on the verge of extinction with almost
no chance of recovery.
Use your consumer power to demand PBDE-free products. Choose furniture, carpet and electronic products
that do not use these hazardous chemicals.
Reduce the use of hazardous chemicals by choosing household cleaners, pesticides and fertilizers which are
not toxic to your surroundings. If chemicals are toxic to the oceans, they are also a danger to you and your family.
Support companies that make clean products and consume less pesticide-dependant foods thereby reducing the
amount of pesticides used.
Compost your household, kitchen and yard wastes, which makes an excellent fertilizer.
Never burn treated wood and trash. This releases POPs into the environment.
Recycle all electronic equipment responsibly.
Never pour any oil or other chemicals onto the ground or into drains. Many of these chemicals make their way
to the ocean. Even if you live far from the ocean, the chemicals from your area can be transported to the ocean
in streams and rivers. Maintain your vehicles to prevent oil from leaking onto the road which will then go down a
drain and into the water.
Recycle all oil and chemicals. Most communities have recycling centers that will accept used oil and other
chemicals for recycling.
Your Voice counts. Citizens can also petition their governments to restrict the emission / dumping of toxic
contaminants into the environment.
Cullon, D.L., M.B. Yunker, C. Alleyne, N.J. Dangerfield, S. ONeill, M.J. Whiticar, P.S. Ross. 2009. Persistent
organic pollutant in chinook salmon (Oncorhynchus tshawytscha): Implications for resident killer whales of British
Columbia and adjacent waters. Environmental Toxicology and Chemistry 28(1): 148-161
Desforges, J.P., Ross, P.S., Loseto, L.L. 2012. Transplacental transfer of polychlorinated biphenyls and
polybrominated diphenyl ethers in arctic beluga whales (Delphinapterus leucas). Environmental Toxicology and
Chemistry 31(2): 296-300.
Ross, P.S., De Swart, R.L., Reijnders, P.J.H., Van Loveren, H., Vos, J.G., and Osterhaus, A.D.M.E. 1995.
Contaminant-related suppression of delayed-type hypersensitivity and antibody responses in harbor seals fed
herring from the Baltic Sea. Environ. Health Perspect. 103: 162167.
Ross, Peter S. 2006. Fireproof killer whales (Orcinus orca): flame retardant chemicals and the conservation
imperative in the charismatic icon of British Columbia, Canada. Can. J. Fish. Aquat. Sci. 63: 224234

Killer whales swim off Harmac pulp mill in Nanaimo. (photo Graeme Ellis)

Concentrations of polychlorinated biphenyls (PCB's) in killer whales and humans.

(photo John



in different
killer whale

and sexes.