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Flexible Polyurethane Foam (FPF) is made by either
the "slabstock" or the molding process. Slabstock accounts
for the largest portion. Molding is primarily used for some furniture
and most automotive cushioning. The slabstock process produces large
continuous buns of foam, which are then converted by various fabricating
processes into the desired shapes and sizes of FPF products.
The slabstock process consists of precisely metering, temperature
controlled ingredients of the formulations to a mixing head and
then depositing the liquid mixture onto a moving conveyor. The chemical
reactions involved generate the foaming mass as well as the heat
necessary to cure the resulting foam. During this reaction the initially
closed cell structure is converted to an open cell structure. The
major ingredients involved are a Polyol , a Diisocyanate (usually
Toluene Diisocyanate -TDI) and water. Other ingredients include
an emulsifier to stabilize the rising foam, several catalysts to
control the reaction rates, and a number of optional ingredients
such as colors, combustion modifying additives, auxiliary blowing
agents, fillers and other materials as needed to achieve special
properties for the FPF.
Toluene Diisocyanate (TDI) chemically reacts with the water to
produce Carbon Dioxide gas (the primary foaming agent) and chemical
structures called ureas. It also reacts with the polyol to produce
chemical structures called urethanes that give the product its name.
All of these reactions are precisely controlled to form the desired
FPF product. Many different types of FPF for a large variety of
end uses are produced by variations in the constituents and formulations
producing the desired physical properties of the end product.
It is common practice for a foam machine during a daily production
run to produce a large number of different foams by such variations
without shutting down the machine between production of different
grades.
FLEXIBLE FOAM USES
The number of end uses for FPF is virtually infinite. The largest
volumes are in the area of carpet padding, upholstered furniture,
automotive and bedding followed by many others including sponges,
toys, packaging, sound deadening etc.
The area of carpet padding deserves special mention. In addition
to the slabstock process outlined above the majority of this product
(there are many different grades) is made from scrap foam by mechanically
chopping it into small pieces and rebonding the mixture into new
blocks of foam, which are then cut into desired length and width
as needed. In the US this process consumes virtually all of the
scrap generated during both the manufacturing and fabrication steps
and thus keeps that scrap out of the waste stream. Demand for scrap
is large enough that large volumes of foam scrap are imported into
the US for the manufacture 0f carpet pad. More recently post consumer
scrap recycling; particularly of used carpet padding has been feeding
the rebond process.
Further growth for recycling of FPF is limited by the ability to
economically collect the post consumer scrap. This is a major problem
in the USA. Automotive scrap recovery is developing particularly
in Europe. (See also section on recycling below.)
FLAME RETARDANTS - COMBUSTION MODIFIERS
Although the term "flame retardants" is often used, the
polyurethane foam industry prefers the term "combustion modifiers"
(CM) to avoid giving the impression that CM containing FPF products,
like any carbon containing compound, will not burn. CM containing
FPF products will burn when they are exposed to a sufficiently intense
ignition source.
Consumer activism and concern about flammability of various standard
household and automotive items int the late 1960s resulted in various
regulations at both the state and federal levels. Early standards
to define performance from exposure to small ignition sources included
the Federal Mattress standard (cigarette smoldering only), automotive
(FMVSS 302), and a number of others. A voluntary industry standard
developed by the Upholstered Furniture Action Council (UFAC) has
been in effect for many years controlling the potential for cigarette
ignition of upholstered furniture. The growing use of FPF as major
items of the construction of these consumer items prompted review
of their impact on the flammability characteristics of the item.
Most of these early regulations either did not require use of combustion
modifiers or only small amounts in the FPF used to make the item,
although some others such as the Underwriters Standard 94 for use
in the vicinity of electrical equipment required larger amounts
of CM additives.
The CM additives used initially were mainly compounds called aliphatic
chlorinated phosphate esters, because they worked and were compatible
with foam processing, although they tended to produce undesirable
softening and some degradation in other performance requirements.
They also tended to produce internal "scorch" or discoloration
during manufacture of the foams.
The advent of the California furniture standard (Cal TB 117) which
required both smoldering resistance and resistance to a small open
flame ignition source substantially increased the amount of combustion
modifiers used by the FPF industry. The availability of pentabromodiphenyl
oxide (Penta) in a mixture with an aromatic phosphate ester led
to its acceptance in the industry because of improved physical performance
and resistance to scorch. Because of the nature of the production
process as described above the trend is to use only one combustion
modifier for all products needing to be combustion modified.
The advent of regulations such as California TB 133, Boston Fire
Code, NY Port Authority, FAA etc all of which required much greater
resistance to ignition for finished items used in more hazardous
applications were the driving force for developing improved performance
foam types by use of much larger amounts of combustion modifiers
(Penta) and other additives.
All in all the choices of CM materials suitable for use in flexible
polyurethane foams have been small due to the combined requirements
of combustion modifying performance, compatibility with the foaming
process and effect on physical properties and aging performance
of the foam. Although many materials have been tested over the years
the major technology still involve use of halogenated (chlorine
or bromine containing) compounds in conjunction with organic phosphorus
compounds such as phosphate esters. Other materials that have been
evaluated individually are generally not able to provide the combustibility
performance provided by the halogenated and phosphorus compounds
when used by themselves. These alternatives include such additives
as melamine and aluminum hydrate which are used in combination with
the above systems. Some special high performance FPF products include
use of special expandable graphite or large amounts of melamine
or hydrated alumina in combination with halogenated and phosphorus
compounds. Other additives known in to be used other types of plastics
such as borates have so far not been found effective in flexible
foams. Nanotechnologies have been evaluated and found completely
unsuitable in the FPF production process. The high performance FPF
products generally require high levels of additives and higher than
usual densities both of which result in substantially higher than
normal costs as well as reduced physical properties. These penalties
are accepted because of the need for the higher resistance to ignition
that some specific end uses require.
We do not have data on the amounts of various combustion modifiers
by different producers or by product type, because this information
is proprietary to the foam producers and not available to the PFA.
The qualification process for a new additive is extremely complex.
Once flammability performance under one or more requirements is
established in small-scale experimentation the development process
begins on a larger (and more expensive) scale. Performance in full
scale production runs are needed to obtain data on resistance to
scorch formation and effect on physical properties, particularly
any tendency to soften the foam or to affect aging and potential
degradation during intended use. The latter two are particularly
problematical because a particular grade of foam may be used in
many different end uses.
The question probably most often asked is for alternative methods
of achieving the desired results of flammability performance for
the end use consumer item. Such approaches as use of special fabrics
and/or interliners have utility and drawbacks and are limited to
the areas of furniture and possibly bedding, which involve combinations
of fabric and foam. In those cases it is important to distinguish
between the requirements of the filling material (foam) and the
composite finished product (foam and fabric). There are many problems
in this area including unpredictable synergistic effects (two "good"
materials when combined may have bad performance characteristics).
It has also to be remembered that some existing regulations require
testing performance of both the individual components and the final
composite (for example Cal TB 117, MVSS 302), thus still requiring
the use of additives in the foam component.
The question of how a combustion modifying additive work also needs
to be addressed. In this discussion we can only address the performance
of the foam component and not the much more complex issue of the
composite systems. There are basically two mechanisms involved.
One involves the decomposition of the additive(s) by the heat of
the ignition source and beginning of the burning of the product.
The decomposition fragments in turn quench flame propagation in
the vapor phase above the product. In addition coadditives such
as melamine produce a molten mixture of partially degraded foam
and melamine that is difficult to ignite or burn.
The other major approach uses additives such as inorganic phosphates,
hydrated alumina or specially prepared graphite flake which produce
a solid carbon foam char which prevents further decomposition of
the underlying foam. It has to be remembered that these two approaches
to the problem are incompatible and cannot be used in a single system.
For example a foam containing Penta and melamine will lose its flammability
performance and burn well if a charforming additive such as hydrated
alumina is added. In the limited application case of foam and fabric
it is generally ineffective to combine a melting foam with a melting
fabric or a charforming foam with a nonmelting or charforming fabric.
The choice of approach to CM formulations is dictated mostly by
the required FPF product performance, always remembering that the
foam is only one component of the whole composite system - such
as a piece of furniture. In general foam producers prefer liquid
CM additives because of the greater ease of processing on standard
foaming equipment. Where needed solid additives can be used but
processing is more difficult and these additives give lower strength
properties and are most often used only in high performance products.
There are some significant differences in CM additive use between
the US and European countries. Use of additives in the USA has historically
been much larger (particularly in furniture) because of regulatory
requirements. In Europe use varies widely between countries, with
Great Britain having a strict furniture requirement, some other
EU countries requiring a lesser degree of performance and others
such as Germany preferring that no additives be used in any plastic
product. For any country that does not demand flammability resistance
for their consumer endues items there still is a need for treated
products for export to the US (such as for example in passenger
automobiles or for furniture for export to California). A further
difference between the USA and Europe is the greater use of "polymeric
MDI" (a different isocyanate) in Europe. MDI is little used
in the USA for slabstock FPF. These approaches are practical only
for higher density foams and also produce foams of lower tensile
strength and elongation and therefore have only found limited use.
FOAM RECYCLING
There are two major sources of scrap foam that have to be considered
separately. The first is scrap foam produced during foam production
and fabrication; the second one is foam from products at the end
of their useful life.
Production scrap comes from startup and shutdown of the production
line and from blocks of foam produced during on the run formulation
changes during the production day. More scrap results from fabrication
as the foam blocks are cut or shaped into desired end products.
All of these foams are good materials but cannot be used for regular
production orders.
Historically in the US all of this type of scrap has been recycled
by shredding the foam into small pieces and rebonding the shredded
mass into molded large blocks. These are then converted to long
rolls of foam laminated with a film and used as carpet padding.
Some shredded foam is also used as filler for pillows or as soft
filling for furniture backs. The use as carpet padding is mostly
limited to the USA for the major market of wall-to-wall carpeting.
In addition to utilizing the production scrap originating in the
USA this end use has also consumed large amounts of imported production
scrap originating in Europe and elsewhere. Over the last few years
post consumer scrap has become available in significant amounts
mainly from used carpet padding. These materials are also recycled
into new carpet padding. Shredding and rebonding is done by a number
of foam producers.
More recently the feasibility of grinding FPF to produce a very
fine powder, which can be added as filler to new foam, has been
established and commercialized, but it is still in the early growth
stages. Such fillers can be incorporated into new foam at a level
of up to 15 %.
Chemical degradation schemes for scrap foams to recover some or
most of the raw materials have been investigated intensively but
so far has not been established as a significant commercial process.
Energy recovery by incineration is eminently appealing but has
not made a significant impact for the same reasons it is not a preferred
approach for other materials.
In all cases of foam recycling the end products must be checked
for manufacturing and end product performance including flammability.
No major problems have been found.
The major problem with expanding use of recyclable materials is
the process of collecting it and separating it from contaminants
and transporting it to the scrap utilizing facilities in an economic
manner. Greater availability of recovered scrap in the automotive
industry is expected over the next few years as pending requirements
in Europe take effect.
As far as BFR's such as Penta is concerned it should be remembered
that the major end use in furniture is only about 20 years old and
considering the average life cycle of furniture to be 15 - 25 years
little foam scrap containing this material would be expected to
be in landfills at this time.
BFR ALTERNATIVES
The major question is - what are they and how do they perform?
One option is to go back to the older technology of using chlorinated
phosphate esters. These are effective as combustion modifiers but
have the problem of producing scorch in low-density foam formulations.
Since they are more volatile and somewhat less stable than such
products as Penta they pose developing problems in automotive end
uses because of restrictions on volatile emissions ("fogging")
and in noise deadening applications (office equipment, large computers
etc because of potential corrosion.
Other CM products under evaluation include non-halogen (chlorine
or bromine) containing phosphorus additives and some reactive bromine
compounds. None of these have reached large-scale applications trials.
In all cases the effect on finished FPF product performance, including
aging, has to be established for each consumer end use item for
which it is intended. In the development of new additives preference
is still for liquid high boiling products. Because of the many performance
requirements and large number of end uses the choice of potential
new CM additives is limited and becomes even more restricted if
the choice has to be a non halogen-containing compound. Of course
it will also be necessary for each possible alternative to establish
that it does not present an environmental problem equal to or worse
than the current situation. There are no expected major problems
affecting recyclability if they meet the other requirements. Cost,
which is a major consideration for most applications, is unknown
at this time.
In may also be worthwhile to continue investigation of barrier
fabric technology for upholstered furniture and bedding as a possible
alternative to the use of CM additives. This, of course, would require
additional revision of California TB117.
Thank you for the opportunity to make this presentation.
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