Flame and Smoke Retardants

in Vinyl Chloride Polymers –

Commercial Usage
and Current Developments
EDWARD D. WEIL*
Polytechnic University
6 Metrotech Center
Brooklyn, NY 11201, USA

SERGEI LEVCHIK AND PAUL MOY

Supresta U. S. LLC
Ardsley Park
420 Saw Mill River Road
Ardsley, NY 10502, USA
(Received March 21, 2005)

ABSTRACT: The flame and smoke retardance of polyvinyl chloride (PVC) is

reviewed with emphasis on the chemical additives used to achieve acceptable
fire properties in the principal application areas. Particular attention is given to
the current ‘state-of-the-art’ of vinyl compounding in regard to the chemicals
used. Representative formulations are shown for several of the main applica-
tions of PVC.

KEY WORDS: polyvinly chloride, flame, smoke, plasticizers, chloroparaffins,

antimony oxide, phosphates, borates, molybdates, alumina trihydrate,
magnesium hydroxide, safety.

INTRODUCTION

POLYVINYL CHLORIDE IS the world’s third largest plastic in terms of sales

volume. Its success is the result of low price, extraordinary versatility and

*Author to whom correspondence should be addressed. E-mail: [email protected]

JOURNAL OF FIRE SCIENCES, VOL. 24 – May 2006 211

0734-9041/06/03 0211–26 $10.00/0 DOI: 10.1177/0734904106057951
ß 2006 SAGE Publications

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

212 E. D. WEIL ET AL.

stability to weathering. By means of plasticizers, the hardness and

flexibility can be varied over a wide range. It is largely used as a homo-
polymer but the vinyl chloride–vinyl acetate copolymer is also of some
significance. The topic of flame and smoke retardance of PVC has been
reviewed by Nass and Heiberger [1] in a four-volume encyclopedia
published in 1997. The topic of fire performance of PVC has recently been
reviewed by Hirschler [2]. In the present review, information not
specifically referenced has been derived from commercial product
literature.

FIRE PROPERTIES OF PVC

Polyvinyl chloride does not exist as the pure substance other than
at a polymerization site. Neat PVC, i.e., rigid or unplasticized PVC,
is difficult to ignite, and will cease burning as soon as the source of heat
or flame is removed. Neat PVC has 56.8% chlorine content and an
oxygen index of about 47, compared to most non-halogen polymers,
which have oxygen indices ranging from 17.4 (polypropylene or
polymethyl methacrylate) to 26 (polycarbonate). Even in dry powder
form, PVC is ignition-resistant, relatively safe to air-convey without
serious risk of dust explosions unless admixed with more combustible
powders. The fire behavior of PVC has been extensively studied.
When PVC is thermally decomposed or exposed to flames, it
dehydrochlorinates and the chlorine content gets converted to hydrogen
chloride gas, which can be emitted into the vapor space or retained in
the condensed phase if a base such as calcium carbonate is present
to produce calcium chloride. However, unlike carbon monoxide,
the hydrogen chloride concentration quickly declines as it is absorbed
on surfaces, and it usually does not travel far [2].
Unplasticized PVC softens as it is heated and as it burns. Generally, it is
difficult to ignite and it readily self-extinguishes. The net heat of
combustion is 16.9 kJ/g, whereas most other plastics are in the range of
24–43 kJ/g. The minimum radiant flux for ignition is about 21 kW/m2.
The self-ignition temperature is 507
C. Hydrogen chloride gas begins
to be evolved at the 227–277
C range for pure PVC; but this temperature
is greatly affected by stabilizing or destabilizing additives. Because of its
high content of chlorine, which is a non-contributor to the heat of
combustion, the heat release characteristic of unplasticized PVC is the
lowest of all commodity plastics. Also, the flame spread rates of rigid PVC
formulations are much lower than wood and most other polymers, for
example as measured by the ASTM E 162 or E 84 test methods [2].

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

Flame and Smoke Retardants in Vinyl Chloride Polymers 213

Unmodified PVC is a stiff brittle material and it is never used as

an uncompounded polymer. Rigid PVC formulations (i.e., with 0 to
about 10 phr plasticizer) generally require processing aids, stabilizers,
and often impact modifiers, such as acrylate polymers. Rigid PVC
finds use in pipes, pipe fittings, extruded profiles for gutters, siding,
window frames, fencing, decking, electrical equipment housings, blister
packages, and thermoformed containers. In building applications, PVC
is probably the most widely used plastic. It has reasonably good
ultraviolet light stability (dependent on pigment) and fair heat stability.
Its softening temperature can be raised by blending, for example, with
ABS or ASA. In terms of the flame spread test ASTM E-84
(Steiner tunnel) used for building code requirements in the US, rigid
PVC achieves a flame spread index of Class 1, i.e., a flame spread index
less than 25, compared to the reference for wood, which is rated at 100.
However, the smoke developed index of rigid PVC tends to be poor,
unless smoke suppressant additives are used, as discussed below. For
many applications, there are no flammability or smoke regulations, or
such lenient standards that the usual PVC formulation is adequate.
A rather new use for rigid PVC (and other plastics) is in pallets, as a
replacement for wood. The flammability requirements for this applica-
tion tend to be based on the fire performance of wood. Because of the
stacking of pallets in warehouses and storerooms, there should be
stringent flammability requirements, which are likely to favor PVC over
other inexpensive plastics, but requirements seem not to be fully in
place as yet.
Polyvinyl chloride compounds are now extensively used for cable
jackets and primary electrical insulation. Such compounds can even be
used for the relatively demanding plenum applications, where they must
meet the requirements of the UL 910 test, recently replaced by the NFPA
262 test (which has both flame propagation and smoke limitations). This
use was developed in the last two decades and has advantages in relative
cost (compared to fluoropolymers), and ease of processing. The major
disadvantage has been smoke obscuration and that has been met by
improved additive systems. Flexible PVC systems with flame-retarding
and smoke-retarding additives are discussed below.

PLASTICIZED (FLEXIBLE) PVC

The fire properties of plasticized PVC are largely determined by

the type and amount of plasticizer. The plasticized formulations
comprise the largest use of PVC, for wire and cable, packaging films,

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

214 E. D. WEIL ET AL.

flooring, upholstery, roofing membranes, wall covering, pool liners,

shower curtains, apparel, greenhouses, geomembranes, automobile
parts, conveyer belts, toys, and bottles. Some of these applications
require flammability limitations and some have smoke limitations
as well. Typical plasticizers are dialkyl phthalates, especially ‘dioctyl’
phthalate (more properly bis-2-ethylhexyl phthalate), diisononyl
phthalate, and diisodecyl phthalate. Vinyl flooring often contains butyl
benzyl phthalate, which better resists the dark marks which are caused
by heels. Other plasticizers are also esters; trimellitates (which have
lower vapor pressure than the phthalates), adipates, sebacates, citrates,
and oligomeric or polymeric polyesters [1].
The typical ester plasticizers are volatile enough to be emitted from
the vinyl when it is strongly heated by a flame, and they are all
flammable under these circumstances. There are two traditional
approaches taken to reduce the flammability of plasticized PVC,
namely, the use of antimony oxide and the use of less flammable or
non-flammable plasticizers, namely phosphate plasticizers and tetra-
halophthalate plasticizers discussed below. Recent trends have been in
the direction of higher molecular weight, less volatile plasticizers,
sometimes bromine-containing. With such approaches, the flame spread
and heat release can be comparable to that of unplasticized PVC or even
of fluorinated elastomers [2].

ANTIMONY OXIDE AND RELATED PRODUCTS

Antimony oxide (antimony trioxide, Sb2O3), although usually not

effective as a flame retardant in the absence of halogen, is a powerful
synergist in halogenated polymers such as PVC. It is typically used in
the range of 3–7 phr (rarely as much as 12 phr). It is generally believed to
act mainly by means of its reaction with HCl to form antimony
trichloride which is volatile at fire-exposure temperatures and which
acts as an active flame poison. Antimony oxide is a stable white powder.
The main source at present is China where it occurs as the sulfide ore,
stibnite. Some production of antimony oxide occurs in North America
from imported ore, but a large amount of antimony oxide is imported
ready to use as a flame retardant synergist for plastics. A typical particle
size range is 1.0–1.8 m, more broadly, 0.1–2 m. Larger particle size
product is available (for example Laurel Industries’ THERMOGUARD L
with a particle size of 2.0–3.2 m), which can be used to lessen the
pigmentation effect. On the other hand, the use of a fine particle size

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

Flame and Smoke Retardants in Vinyl Chloride Polymers 215

antimony oxide, an example being Laurel Industries’ ULTRAFINEÕ II,

can provide improved physical properties.
The pigmentation effect can be avoided by use of the more costly
antimony pentoxide, a colloidal powder produced by precipitation
from sodium antimonate solution. Its submicron size is too small to
scatter light and thus allows for translucent or even transparent vinyl
compounds, with no effect on color matching. Sodium antimonate itself
can be used, with the possible advantage of lower smoke [3].
A dust problem associated with antimony oxide, occasionally causing
respiratory or dermal irritation, has been solved by addition of mineral
oils or plasticizers to make dust-free grades, or by pelletizing.
Various grades of antimony oxide are marketed for use in PVC.
A good quality grade has uniformity of crystal size and cubic shape,
which enhances dispersion, improves compounding properties, and
provides improved batch-to-batch consistency. Certain trace impurities,
such as selenium, cause discoloration and the use of grades having high
levels of these impurities should be avoided. The powdered version
of antimony oxide in Europe has an ‘R40’ label (‘limited evidence of
a carcinogenic effect’), but a risk assessment is underway at this time;
the most current reports and the regulatory status of antimony oxide
are available from the International Antimony Oxide Industry
Association on-line newsletters.
Antimony oxide is also available in admixture with other inorganic
materials. For example, Arkema’s THERMOGUARD CPA is a mixture
of antimony oxide, barium sulfate, and zinc sulfide. This product has
been on the market for some decades, and has offered a price advantage
for some vinyl formulations. The zinc sulfide component contributes
some flame retardant synergism and smoke reduction. Formulators can
obtain the zinc sulfide–barium sulfate combination as lithopone, which
also serves as a white pigment, and can be used in addition to antimony
oxide or as a partial replacement.
Some commercial pelletized mixtures of brominated flame retardants
and antimony oxide are available and are said to avoid dust and provide
easier handling.
The interaction of antimony oxide with phosphorus-based flame
retardants is discussed below. Such combinations are often used, but
some degree of antagonism may be found. The topic of antimony-
phosphorus antagonism has been reviewed in [4].
The use of antimony oxide in PVC generally elevates the smoke level
relative to the mass burned in small-scale tests, but on the other hand,
the total smoke may be lowered in a large-scale test or in an actual fire
because of the reduction in the amount or rate of polymer burning.

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

216 E. D. WEIL ET AL.

Table 1. Properties of FR-PVC using dioctyl tetrabromophthalate with 15 phr

antimony oxide and 5 phr Pb stabilizer at 100 parts of PVC (GEON 30).

Formulation 1 2 3 4 5

Dioctyl tetrabromophthalate – 20 40 60 93.4

Trioctyl trimellitate 60 47.2 34.3 21.5 0
Tensile modulus 1640 1740 1760 1830 1980
Tensile strength (at break) 1860 1880 2050 2320 2520
Tensile elongation (%) 308 286 278 263 239
Low temperature brittleness (
C) 22 20 14 14 6
Shore ‘A’ hardness 88 88 88 90 92
LOI (O2%) 27 31 33 36 42
NBS smoke
Smoldering (Dmc) 200 190 180 170 140
Flaming (Dmc) 450 450 440 180 170

HALOGENATED PHTHALATE PLASTICIZERS

The principal product of this family is dioctyl tetrabromophthalate,

available from Great Lakes Chemical as DP-45. It is highly effective as a
flame retardant with relatively low smoke production. It is usually used
in combination with antimony oxide and other additives. One advantage
is that dioctyl tetrabromophthalate has very low volatility and is very
thermally stable, with only 5% weight loss at 290
C, well beyond the
processing range of PVC. It is used in high-end vinyl applications, such
as plenum wiring and railway passenger coach wiring. It can also be
used together with the phosphate esters and ONGARD 2 (a proprietary
MgO–ZnO-based composition made by Great Lakes Chemical) and zinc
borates. Some suggested formulations and their properties are given
in Table 1.
Unitex claims that a mixed halogen (bromine–chlorine) phthalate
ester has improved flame retardancy and mechanical properties.
This is probably a blend of dioctyl tetrachlorophthalate and dioctyl
tetrabromophthalate. Some evidence for bromine–chlorine synergism
has been discussed in a broad review on flame retardant synergism in [4].

CHLORINATED PARAFFINS

These are old products with recently improved stability. They are
used as secondary plasticizers and as sources of supplemental chlorine
content. They are also relatively low in cost compared to the flame

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

Flame and Smoke Retardants in Vinyl Chloride Polymers 217

retardant phosphate plasticizers, which they can partly replace.

Chloroparaffins are useful in formulating for relatively low smoke.
Early versions had marginal thermal stability but newer grades from
Dover Chemical have been much improved in stability by use of lower
temperature chlorination conditions, choice of substantially unbranched
paraffin feedstocks, and inclusion of an effective stabilizer package [5].
A typical product of this type is Dover’s DG50, which has an average
composition approximating C14H24Cl6. Cost savings can also be achieved
by replacing part of the antimony oxide or phosphate plasticizer in
a PVC formulation by chlorinated paraffin. For example, a formulation
of 50 phr dioctyl phthalate and 8 phr antimony oxide can be replaced
with 40 phr dioctyl phthalate, 12 phr chlorinated paraffin, and 4 phr
antimony oxide, with similar performance and some cost savings.
Likewise, a formulation of 30 phr calcium carbonate, 3 phr antimony
oxide, 15 phr dioctyl phthalate, and 35 phr octyl diphenyl phosphate can
be replaced, as suggested by Dover, with 30 phr calcium carbonate, 3 phr
antimony oxide, 25 phr octyl diphenyl phosphate, and 12 phr chlorinated
paraffin (Dover’s DG50) with cost savings but substantially equivalent
physical properties.
To avoid migration and exudation, the level of chloroparaffin must be
limited, the limit depending on the primary plasticizer. With dioctyl
phthalate, the chloroparaffin (such as Dover’s DG 50) should not exceed
20 phr whereas with diisononyl phthalate, the chloroparaffin should
not exceed 16 phr. Higher levels of chloroparaffin can be used when
a primary plasticizer is an aryl phosphate.
Toxicological and aquatic toxicity concerns have been avoided by the
longer chain length paraffins and by chlorination to a higher level.
Polychlorinated polyethylenes, such as TYRIN (DuPont Dow
Elastomers) can also be blended with rigid PVC to afford good low
temperature impact and ductility, good retention of strength and
weatherability without loss of flame retardancy.

INORGANIC FLAME RETARDANTS,

SYNERGISTS, AND SMOKE SUPPRESSANTS

Alumina Trihydrate (Aluminum Hydroxide, ATH)

This additive is part of the flame retardant system of many rigid and
semi-rigid vinyl formulations. It is inexpensive on a per-pound basis
but rather high loadings must be used, and its density causes the
formulation to be less favorable in cost on a volume basis. Wire, cable,

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

218 E. D. WEIL ET AL.

and flooring formulations are its largest uses. The power cable segment
is growing rapidly particularly in Asia, the telecom segment less so.
Aluminum hydroxide acts as a heat sink when the formulation is
exposed to flame, by virtue of its endothermic release of water starting
at about 204
C, and consuming 1051 J/g of ATH. The released water
also dilutes the organic fuel released from the formulation, reduces the
oxygen concentration in the flame zone, and has a cooling effect on the
flame. The layer of dehydrated alumina offers a barrier to heat and
mass transfer. Frequently, this barrier is bolstered by the presence of
carbonized material, and may also be improved by the presence of fluxes
and sintering components, such as zinc borate.
Plasticized PVC containing typical phthalate plasticizers generally
produces dense smoke, although this can be alleviated by further
additives, as discussed below. The smoke emission is aggravated,
particularly under flaming conditions, by the presence of antimony
oxide but alleviated by the addition of ATH. Various other smoke-
reducing additives will be discussed below. Data from Albemarle show
substantial reduction of smoke levels from PVC containing ATH,
in comparison to antimony oxide formulations at the same level of
flame retardancy. Obviously, to reach the same flame retardancy,
the ATH percentage must be much higher than the antimony oxide
percentage.
Typical PVC cable formulations are presented in Table 2. Some other
useful starting-point formulations are as follows: for thin rigid vinyl
protective films: 100 phr PVC, 15 phr ATH or 8 phr ATH plus
2 phr Sb2O3 plus 2 phr ONGARD 2. For flooring: 100 phr PVC, 100 phr
ATH plus 80 phr phthalate plasticizer plus stabilizer as needed.

Table 2. Typical PVC cable formulations.

Components (and resultant properties) Quantity (phr)

PVC (K value ¼ 70) 100 100

Diisononyl phthalate 55 55
Calcium carbonate (e.g., OMYA EX H1SP) 10 10
ATH (e.g., MARTINAL OL-104E) 50 40
Antimony oxide – 5
Lead-based stabilizer 4 4
Lubricant (e.g., A-C 6A) 0.5 0.5
Properties
LOI (ASTM D 2863-77)(% O2) 27 31
Tensile strength (DIN 53504) 17.5 MPa 16 MPa
Elongation at break (DIN 53504)(%) 220 250

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

Flame and Smoke Retardants in Vinyl Chloride Polymers 219

For wall covering to meet LOI of 27%, DIN 4102: 100 phr PVC, 34 phr
ATH, 20 phr phosphate plasticizer, 3 phr epoxidized soy bean oil, 1 phr
Sb2O3, and 2 phr stabilizer. For carpet backing (PVC foam coatings):
100 phr PVC, 60 phr ATH, 80 phr plasticizer (presumably a phthalate)
and up to 5 phr stabilizer. For conveyer belts: 100 phr PVC, 40 phr ATH,
10 phr calcium carbonate, 50 phr phosphate plasticizer, 4 phr Sb2O3, and
stabilizer as required. For coated fabrics such as awnings, tarpaulins,
inflatable structures: 100 phr PVC, 40 phr ATH, 45 phr phosphate
plasticizer, 18 phr dioctyl phthalate, and stabilizer as required.
A major challenge is to incorporate enough ATH to achieve the
desired flame retardancy while retaining useful flow properties and
mechanical properties (especially flexibility). Plasticized PVC is rather
‘forgiving’ and ground ATH can be used as well as the precipitated
grades. However, the selection of ATH is more demanding in rigid
and semi-rigid formulations. A variety of particle sizes, surface
treatments, and particle morphologies is available. Both reprecipitated
(from commodity grade ATH) and milled products are available.
As a rough guide to the selection, the larger particle size range is
preferred when rapid mixing and melt flow is required. The finer
particle sizes are generally slower to disperse but may be found to have
somewhat higher flame retardant effect, somewhat better tensile, and
somewhat better tear strength [6].
Fatty acid surface-treated grades, such as MARTINAL OL-104C and
OL-107C are more dispersible, give lower viscosity and increased
flexibility in PVC. Surface treatment with silanes is available also, and
may provide even better mechanical properties, especially in PVC alloys,
such as GE’s CYCOVIN alloy of PVC with ABS. In highly filled PVC,
where lubricity and melt flow must be maintained, some proprietary
coated ATH grades are available from Albemarle and Huber.
Aluminum hydroxide can somewhat compromise the heat stability
of rigid PVC [7]. Adjustments in stabilizer content may be helpful.

Magnesium Hydroxide and Related Magnesium Minerals

Magnesium hydroxide occurs in crude form as the natural mineral

brucite, and in finely ground form, has some usage as a low-cost plastics
additive. However, magnesium hydroxide usually is employed as much
purer synthetic products. Moderately priced grades are available from
Martin Marietta as MAGSHIELD and from Albemarle as MAGNIFIN.
Higher priced magnesium hydroxide with lower surface reactivity, or in
some cases coated surfaces, and more compact particles are available
as KISUMA grades from Kyowa (Japan). Magnesium hydroxide is often

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

220 E. D. WEIL ET AL.

used in rigid PVC where the processing temperature exceeds the

dehydration temperature of ATH (above about 200
C). Magnesium
hydroxide loses its one molar equivalent of chemically bound water in
the range of 300–400
C, and absorbs 1316 J/g (somewhat above the
dehydration endotherm of ATH). Processing of formulations containing
magnesium hydroxide can be carried out at higher temperatures than
with ATH, limited mainly by the dynamic stability of the PVC.
Magnesium hydroxide is usually found to be more effective than ATH
as a smoke suppressant. Because of its basicity, it also scavenges
hydrochloric acid and thus makes the smoke less corrosive.
Besides magnesium hydroxide itself, basic magnesium carbonate
(hydromagnesite) or huntite (a magnesium calcium carbonate) or blends
thereof, have been used for many years as smoke suppressants in
flexible PVC, typically at 5–20% in combination with alkyl diphenyl
phosphate plasticizers [8,9]. Basic magnesium carbonate is usually
somewhat hygroscopic and needs to be kept dry to avoid porosity in the
compounded vinyl.
ULTRACARB (Minelco) is a natural mineral, which is a mixture
of huntite, Mg3Ca(CO3)4 and hydromagnesite, Mg4(CO3)3(OH)2  3H2O.
In an extensive optimization study, ULTRACARB was shown to be
effective in formulating low-smoke antimony oxide-free vinyl formula-
tions containing phosphate and brominated phthalate plasticizers.
It was also found that blends of ULTRACARB with calcium carbonate
could be used to obtain flame retardant plasticized formulations with
low acid fume release [9].
Combinations of ATH and Mg(OH)2 are sometimes used to give
protection over a wider temperature range or longer time, and in some
cases appear to show synergism.
ONGARD 2 (Great Lakes Chemical) has been used as an effective
smoke and flame suppressant, particularly in combination with alkyl
diphenyl phosphates in flexible PVC. An example of the high flame
retardant effectiveness of ONGARD 2 at 2 phr in combination with
antimony oxide at 2 phr in rigid PVC pipe was shown by Morley in
the Wickson formulation handbook [10]. A less abrasive version,
ONGARD 5, has recently been introduced by Great Lakes Chemical.

Molybdenum-containing Additives

Molybdenum compounds are regarded as the standard additives for

low-smoke formulations, the leading additive being ammonium
octamolybdate (AOM) for vinyl applications. Studies have shown that
molybdates work in the solid phase as most of the molybdenum is found

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

Flame and Smoke Retardants in Vinyl Chloride Polymers 221

in the char residue. Molybdates are said to reduce smoke by catalyzing

the formation of trans-olefin structures from cis-olefin structures in the
dehydrochlorinated polymer residue, so that the propensity to cyclize to
soot-forming aromatic species is lessened [11].
Zinc and calcium molybdates are also effective and are available
from Sherwin Williams as KEMGARDS. KEMGARD 981 is zinc
phosphate–zinc oxide, the only non-molybdenum product in the
family. Newer members of this family are KEMGARD MZM, a zinc
molybdate–magnesium hydroxide complex, which gives good smoke
suppression with good dynamic stability in rigid PVC, and KEMGARD
HPSS, a basic zinc molybdate–magnesium hydroxide complex, which
gives good smoke suppression and contributes to flame retardancy with
good dynamic stability in flexible PVC. Favorable smoke comparisons of
these products to ammonium octamolybdate have been published by
Innes and Innes [12].
Physical mixtures of molybdenum trioxide with other metal oxides
(copper, iron, and tin) are also reported to provide low-smoke
characteristics, although there is a color problem with such mixtures.
Molybdenum oxide, copper oxides, and ferric oxide also decrease rate
of heat release and increase char [13] but only molybdenum oxide seems
to have a retarding effect on dehydrochlorination [14].
One product in this group, KEMGARD 911C, comprises an inert filler
(talc) as the core support medium onto which a zinc molybdate layer
is precipitated. This coated core structure effectively provides smoke
suppression at a lower cost than the neat molybdates.

Copper Compounds

Copper salts, particularly copper oxalate in combination with a

molybdate, have been used as smoke suppressants, originally under a
B. F. Goodrich patent [15]. In a later series of studies by Starnes et al.
[16], the lengthening of ignition time and the reduction of mass loss rate
under cone calorimetry conditions have been recognized in addition
to the smoke suppression, and an insight into the modes of action of
copper compounds has been gained. Reductive dechlorination with
carbon-to-carbon coupling is an important feature of this action. Copper
compounds also help the thermal stability of PVC compounds.

Zinc Borates and Barium Borate

These additives are well established in PVC as partial replacement

for antimony oxide with the distinct advantage of relatively lower smoke,

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

222 E. D. WEIL ET AL.

and anti-afterglow action. The most widely used zinc borate is Luzenac’s
(formerly U. S. Borax’s) FIREBRAKE ZB, which is 2ZnO  3B2O3  3.5H2O
and a more finely divided version of the same compound, FIREBRAKE
ZBXF. Other zinc borates which are on the market and said to be
useful in PVC (higher activity claimed due to higher ZnO ratio) are ZnO
B2O3  2H2O and 2ZnO  2B2O3  3H2O (Anzon). The action of all of these
zinc borates is generally believed to be the promotion of cross-linking
and charring, plus the formation of low melting glass, which together
with other inorganic fillers can form a barrier. There is also a small
endothermic and fuel dilution effect as the water of hydration is lost.
Additionally, zinc borate can suppress glowing combustion (smolder-
ing) because it alters the surface morphology of the char. Boron is
known to be an inhibitor of carbon combustion, according to one
hypothesis, by occupying active sites on the graphite lattice [17].
By itself, zinc borate is a less effective flame retardant in PVC than
antimony oxide, but their combinations are very effective (Figure 1).
There are a number of products that can be suitable as low-smoke
additives and/or partial replacement for antimony oxide. Care must
be exercised with these zinc-based materials as they can destabilize
PVC if not properly formulated, and long-term heat stability can be
compromised.

Figure 1. Oxygen indices of flexible PVC formulations.

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

Flame and Smoke Retardants in Vinyl Chloride Polymers 223

A barium borate is available in the market as Buckman’s

FLAMEBLOC, and is said to have some advantages in afterglow
suppression and low water solubility.

Zinc Stannates

Zinc stannate (ZnSnO3) (available from Alcan) and zinc hydroxy-

stannate (ZnSn(OH)6) are colorless water-insoluble salts that are
effective smoke suppressants and flame retardant synergists.
Economics has tended to retard the usage of these compounds.
Zinc hydroxystannate is effective as both a flame retardant and a
smoke suppressant in PVC at about 3 phr and does not impair color or
stability [7,18]. As partial or even complete replacements for antimony
oxide, the stannates are claimed to afford good flame retardancy
(probably by vapor phase action as well as condensed phase action) with
reduced smoke and carbon monoxide production [19]. Very good overall
flame and smoke performance was obtained by an optimized combina-
tion of dodecyl diphenyl phosphate, a brominated aromatic ester
(probably dioctyl tetrabromophthalate), ATH, zinc stannate, ammo-
nium octamolybdate, and antimony oxide [20]. Zinc stannates can also
allow reducing or eliminating the ammonium octamolybdate.

Zinc Sulfide

This is a very inexpensive white pigment which has smoke

suppressant retardant action in PVC. Used by itself, it is not notably
flame retardant but it can replace up to about half the antimony oxide
in a vinyl formulation with retention of flame retardant properties [21].
Zinc sulfide is also available in combination with barium sulfate as
‘lithopone’, which has been used for many years as an inexpensive white
substitute for titanium dioxide.

Calcium Carbonate

Calcium carbonate is usually viewed as a filler rather than as a flame

retardant. Although when heated to 1150
C, it yields CO2 endothermi-
cally, this action occurs at much too high a temperature to help retard
the burning of the polymer, but calcium carbonate does act as a
non-flammable diluent. During burning, calcium carbonate (especially
the precipitated grades which have more surface than the ground
grades) also can capture hydrogen chloride and thus can reduce the
corrosivity of the smoke, as well as provide some stabilizing action.

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

224 E. D. WEIL ET AL.

This important method for decreasing the hydrogen chloride emissions

depends on the fine state of division of the calcium carbonate, and
its adequate dispersion. Stearic acid surface-treated calcium carbonate,
which disperses more easily, is available from a number of suppliers.

Smoke Suppressants – General Comments

Often the effort to lower smoke generation seems counterproductive

to flame resistance, as they can have competing mechanisms. Some
flame retardants can interfere in the combustion efficacy of the volatile
species and cause more airborne soot particles to be formed. Low-smoke
additives can produce more combustible organic gases, which burn more
cleanly but can result in higher heats of combustion and thus negatively
affect flame retardancy. Obviously, the balancing act of low smoke and
high flame retardancy can be difficult to achieve. Formulation studies to
reduce smoke and flammability have been discussed by Innes [22] who
emphasizes the importance of the interactions. In general, it can be said
that a significant decrease in flame spread or heat release is almost
certain to lead to a decrease in total smoke release.

Low Flammability Plasticizers: Phosphate Esters

In flexible vinyl compounds, the greatest source of fuel is the

plasticizer. Non-flame retardant plasticizers, such as polymerics and/
or copolymer systems can contribute to the composite’s ductility. These
alternatives can alter the combustion mechanisms discussed previously
by contributing less fuel than other plasticizers. As mentioned above,
a tetrabromophthalate ester can be used as a flame retardant plasticizer,
especially where low smoke and a high degree of fire retardance is
required (railway cables, for instance). However, the most common
approach is to use organophosphate esters as only part of the plasticizer
system, in view of their higher cost and lower plasticizing efficiency.
The organophosphates are much less combustible than the phthalates.
They have much lower heats of combustion and tend to be moderate
retardants of the flame chemistry. The phosphates, most commonly
blended with dialkyl phthalates, are used in films, cables, conveyer belts,
v-belts, and coated textiles such as tarpaulins.
This application of organophosphates has been known since the
advent of PVC as a commercial product in the 1930s. The earliest
version was tricresyl phosphate made from mixed o,m, p-cresol. It was
discovered in the 1930–1940 period that the ortho-cresyl isomer
made tricresyl phosphates rather strongly neurotoxic, so thereafter,

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

Flame and Smoke Retardants in Vinyl Chloride Polymers 225

only m,p-cresol was used to make these phosphates. The chemistry of

the toxic effect has been well understood to involve the ability of the
ortho-cresyl phosphate structure to be bio-oxidized to a cyclic phosphate,
which can attack the cholinesterase enzyme, although the p-ethylphenyl
group also shows a related toxic effect by a slightly different
mechanism [23].
The cresyl diphenyl phosphate is used more often in Europe and Asia
because of its efficiency and low cost. For most US markets, however,
it is less often used because of volatility and toxicity concerns [24],
although if free of o-cresyl isomer, it is not a serious neurotoxicant.
Triaryl phosphates in the US based on ‘natural cresylics’ are likely to be
tricresyl phosphate.
Trixylenyl phosphates have been used where high temperature
performance is important or long-term heat resistance, such as in
agricultural (greenhouse) film, or in automobile seating where
avoidance of windshield fogging is required.
Tricresyl phosphate replacements have evolved by substituting
the cresol (which has become increasingly costly) by a synthetic
isopropylphenol–phenol mixture to produce a mixed triaryl phosphate,
most commonly approximating diphenyl isopropylphenyl phosphate.
This development was originally driven by the erratic supply and pricing
due to the by-product nature of the cresols (the original coal tar source
dwindled, leaving only a petroleum byproduct source). Although one
study showed the ortho-isopropylphenyl isomer to be the best from
a stability standpoint [25], the commercial products appear to be a
mixture of isomers. The isopropylphenyl phenyl phosphates with lower
and higher levels of isopropyl substitution have been sold as flame
retardant PVC plasticizers, such as Akzo Nobel’s (now Supresta’s)
PHOSFLEX 21P, 31P, and 41P or FMC’s KRONITEX 50 (similar to
cresyl diphenyl phosphate in physical properties) and KRONITEX 100
(similar to tricresyl phosphate in physical properties). FMC triaryl
phosphate products are now made and sold by Great Lakes Chemical as
REOFOS 50, 65, and 95 (from isopropylphenols) and PLIOBRAC CDP,
TCP, and TXP (from cresols and xylenols). Certain products of the
Bayer (Lanxess) DISFLAMMOL family are of this type.
According to an FMC author [26], a typical isopropylphenyl phosphate
consists of 7–30% triphenyl phosphate, 10–20% 2-isopropylphenyl
diphenyl phosphate, 2–3% 3-isopropylphenyl diphenyl phosphate,
10–15% 4-isopropylphenyl diphenyl phosphate, 7–19% di(2-isopropyl-
phenyl) phenyl phosphate, and 25–63% higher alkylated triaryl
phosphates. This author also points out that the isopropylated triphenyl
phosphates are unique compared to tricresyl phosphates in that they

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

226 E. D. WEIL ET AL.

have conveniently high plastisol fusion rates, but somewhat slower than
tricresyl phosphates. In coating fabric, this property is advantageous in
allowing more time for effective coating and penetration. They also have
smaller increases in viscosity in storage, thus better storage stability of
the plastisol [27].
A related product is tertiary-butylphenyl diphenyl phosphate made
from tertiary-butylphenol produced from phenol and isobutylene. This
was originally introduced in the 1970s as a functional fluid (hydraulic
applications) but has also been found useful in PVC. It is available from
Akzo Nobel (now from Supresta) as PHOSFLEX 61B and 71B. By itself,
it has inferior plasticizing activity compared to the isopropylphenyl
homolog, but when diluted with a phthalate plasticizer, its activity is
adequate, and it has some advantages of thermooxidative stability [28].
It has good flame retardant activity and imparts rapid gelation
characteristics to PVC plastisol formulations as well as good resistance
to microbial damage.
The triaryl phosphates are more costly and somewhat less effective as
plasticizers than the common dialkyl phthalate plasticizers. Plasticized
PVC usually is under price constraints, so compounders of plasticized
PVC will typically use mostly the dialkyl phthalate, mixed with no more
of the triaryl phosphate than is needed to comfortably pass whatever
flammability requirements must be met. In general, the more highly
plasticized the formulation, the higher the ratio of phosphate to
phthalate to meet a given flame retardancy; in an unfilled plastisol
system with 80 parts of plasticizer per 100 parts of resin, 25% of the
triaryl phosphate in the plasticizer mix (20 phr) is suggested as a
minimum.

Low Temperature Alkyl Diphenyl Phosphate Plasticizers

The triaryl phosphates impart undesirable stiffness to plasticized PVC

at low temperatures. In the 1950s, Monsanto developed 2-ethylhexyl
diphenyl phosphate (now SANTICIZER 141) and isodecyl diphenyl
phosphate (SANTICIZER 148). Along with SANTICIZER 2148, appar-
ently a variant of SANTICIZER 148, with even lower smoke and better
low-temperature plasticizing properties, these are now available from
Ferro Corp. Products similar to SANTICIZER 141 and 148 were later
available from Akzo Nobel (now Supresta) as PHOSFLEX 362 and 390,
respectively. Octyl (probably 2-ethylhexyl) diphenyl phosphate has been
available from Bayer (now Lanxess) as DISFLAMMOL DPO. These
partially aliphatic phosphates are more plasticizing than the triaryl

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

Flame and Smoke Retardants in Vinyl Chloride Polymers 227

phosphates. Uses are in tarpaulins, automobile seating, flooring,

conveyer belts, and cable sheathing, especially plenum cable jacketing.
They also are said to have advantages in weathering, gelling properties,
and resistance to saponification (by alkaline detergents, for example).
They are somewhat less effective than the triaryl phosphates from a
flammability standpoint but distinctly better in smoke evolution.
A Teknor Apex patent [29] shows the use of pentaerythritol ester
plasticizers (HERCOFLEX) in combination with isodecyl diphenyl
phosphate and a tetrabromophthalate plus other additives, such as
ATH in low-smoke formulations for wire and cable insulation. Data in
this patent show that lowering the tetrabromophthalate and raising the
ATH level is favorable to low smoke in a wire and cable insulation
formulation.

Comparison of Some Flame Retardant

and Non-flame Retardant Plasticizers

Comparative data in Table 3 were selected from a Great Lakes

Chemical bulletin ‘Speciality Plasticizers for PVC’ for a formulation
containing 100 parts of a PVC suspension polymer (viscosity 128 by ISO
R174), 60 phr of the indicated plasticizer, 1 phr IRGASTAB 17M, and
0.2 phr IRGAWAX 0.2.

Table 3. Comparison of PVC formulations using various plasticizers at 60 phr.

Viscosity at Density at Shore A Cold flex Clash Oxygen

Identity of phosphate 25
C (mm/s) 25
C (g/cc) hardness and Berg (
C) index (%)

Isopropylated phenyl 44.5 1.183 74 2 32.6

Isopropylated phenyl 48 1.174 75 2 32.5
Isopropylated phenyl 57 1.164 76 1 32.5
Isopropylated phenyl 93 1.136 78 þ1 32
Cresyl diphenyl 36 1.202 73 4 33
Tricresyl 60 1.158 74 0 32.5
Trixylenyl 95 1.134 76 þ4 32
t-Butylphenyl diphenyl 81 1.165 89 þ11 32
2-Ethylhexyl diphenyl 16 1.087 70 24 28.6
Isodecyl diphenyl 22 1.065 71 20 28.1
For comparison
Dioctyl phthalate 56 0.980 71 24 24
Diisononyl phthalate 85 0.970 75 19 24
Tetrabromophthalate 1036 1.54 94 þ18 37.5

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

228 E. D. WEIL ET AL.

Table 4. Cone calorimetry comparison of PVC with various additives.

Additive Burning Peak heat Time to

level time (s) release rate peak heat Char LOI
Additive(s) to PVC (phr) in cone cal. (kW/m2) release (s) (wt%) (% O2)

Diisodecyl phthalate 50 128 45.1 35 6 23.5

Antimony oxide 6 134 36.8 48 12 29.8
AO/zinc borate (ZB) 6/6 144 42.1 38 22.4 30.5
Triaryl phosphate (TAP) 50 148 40.8 46 7.7 31.8
TAP/ZB 50/6 200 30.6 54 10.8 34.7
TAP/AO 50/6 180 44.4 70 9.2 32.9
TAP/AO/ZB 50/6/6 176 23.9 34 18.3 33.3
TAP/AO/ZB/ATH 50/6/6/30 300 25.4 52 10.5 37.1

Comparison of Various Combinations

of Plasticizers and Other Additives

Some more or less advantageous combinations (from differing

criteria) are shown in Table 4 [30]. The triaryl phosphate (TAP) is
isopropylphenyl diphenyl phosphate. The data were obtained in the cone
calorimeter at 50 kW/m2.
These data show that the preferred formulation should depend on the
criteria used. Some advantage is seen by cone calorimetry in combin-
ing antimony oxide and zinc borate. The combination of the triaryl
phosphate with antimony oxide, while not actually antagonistic, shows a
distinctly less-than-additive effect and is thus relatively inefficient.
On the basis of LOI, zinc borate appears superior to antimony oxide in
combination with the TAP. The presence of ATH produces a possibly
useful slow burning effect.

Formulating for Specific Applications

A still-useful general reference (1993) is a handbook by Wickson [10].

The following formulations are taken from more recent sources.

Calendered Vinyls

For thin film laminates, antimony oxide is frequently used in

combination with other inorganic additives. Alumina trihydrate,
magnesium hydroxide, and zinc borate are the principal choices. All of
these are useful for lowering smoke. Alternatively, phosphate ester
plasticizers are used, again, often with ATH and/or magnesium

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

Flame and Smoke Retardants in Vinyl Chloride Polymers 229

hydroxide. For good smoke suppression, the zinc–magnesia composition

ONGARD 2 or zinc borate can be added. Also, where smoke is an
important criterion, the alkyl diphenyl phosphates are often preferred
instead of the triaryl phosphates.
Different applications have different requirements. Some typical or
‘starting point’ formulations are listed below.
The ASTM E-84 tunnel class 1 requirement for wallcovering on smoke
developed index (almost all vinyls meet flame spread index requirements
of 25) [31] is met by the formulation shown in Table 5. Table 6 shows
formulations meeting the requirements for automobile upholstery to
meet Federal Motor Vehicle Safety Standard 302 [31]. Table 7 presents
a formulation for wire and cable insulation to meet the UL NM cable
requirements [32].
A series of UL approved building wire formulations developed by
Exxon-Mobil for TW (moisture-resistant), THW (hot-water-resistant),

Table 5. PVC wall-covering formulation

for ASTM E-84 class 1.

Component phr

PVC 100
Diisodecyl phthalate 26
Phosphate ester 20
Sb2O3 2–4
Zinc borate 5–10
ATH 10–15
CaCO3 40
Stearic acid 0.3
Stabilizer 3–5

Table 6. PVC automobile upholstery formulation

for meeting MVSS 302.

Component phr

PVC 100
Diisodecyl phthalate 70–80
CaCO3 25–50
Epoxidized soybean oil 5
Stabilizer 3
Sb2O3 1.5–2.0
Zinc borate 1.5–2.0

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

230 E. D. WEIL ET AL.

Table 7. PVC wire and cable insulation formulation

to meet UL NM requirements.

Component phr

PVC resin 100

Plasticizer (7–11 phthalate) 40
Magnesium hydroxide 30
Calcium carbonate 20
Stabilizer 3
Antimony oxide 3
Stearic acid 0.5
Properties
LOI 31.0%
Tensile strength 2610 psi
Tensile modulus 20330 psi
Elongation 139%
Melt flow index 0.9 g/10 min

and THWN/THHN (hybrid nylon conductor insulation/PVC jacket) is

given by Coaker [33]. These formulations use various combinations of
calcined clay, calcium carbonate, and antimony oxide with phthalate or
trimellitate plasticizers. Cable jackets which must pass the more severe
vertical cable tray test UL 1685 for flame spread and smoke release
generally will often include some ATH.

Plenum Wire and Cable

It is typical in the US to place communication, alarm, and signaling

wiring in plenums (concealed spaces, which are also part of the air
distribution system). If such wiring is not very fire resistant, this
practice can cause fire and smoke to spread rapidly and stealthily
through a building. Extremely severe fire and smoke requirements,
generally based on the NFPA 262 tunnel test, have been imposed where
wire and cable are not protected by metal conduits or sprinklers. The
challenge to vinyl formulators has been to reach flame and smoke levels
to compete with the expensive fluoropolymer-coated constructions.
Some PVC formulations have been recommended for plenum use,
for example the one provided, in Table 8, in a 1993 patent of the
Belden Division of Cooper Industries [34].
More recently, various alloys of PVC with thermoplastic elastomers
have been shown to have good flame and smoke properties suitable for
plenum applications [2]. These vinyl-based products are said to compete
with fluorinated polymer (FEP) coatings under present codes and

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

Flame and Smoke Retardants in Vinyl Chloride Polymers 231

Table 8. PVC plenum wire formulation for low flammability and low smoke.

Component Parts by weight

PVC (GEON 30) 100

SANTICIZER 2148 phosphate plasticizer 30
Dioctyl tetrabromophthalate 20
Epoxidized soybean oil 3
Alumina trihydrate 30
Ammonium octamolybdate 30
Zinc molybdate 10
Tribasic lead sulfate 7
Stearic acid 0.5
Paraffin wax 0.5

Table 9. PVC blend plenum wire starting-point formulations.

Component A phr B phr C phr

PVC 100 100 100

ELVALOY HP-441 (DuPont ethylene–acrylate–CO) 15 15 15
Dodecyl diphenyl phosphate plasticizer 10 10 10
Dioctyl tetrabromophthalate plasticizer, f.r. 25 25 25
Alumina trihydrate 40 40 40
Huntite–hydromagnesite mix 10 10 10
Hindered phenolic stabilizer (Ciba) 4 4 4
Tribasic lead sulfate stabilizer 3 3 3
Antimony trioxide f.r. synergist 3 3 3
Ammonium octamolybdate (AOM, anti-smoke) 25 10
Zinc stannate (ZS, f.r. synergist and anti-smoke) – 25 15
Cone calorimetry data at 40 kW/m2
Time to ignition (s) 897 705 Never
Peak rate of heat release (kW/m2) 35 35 –
Average specific extinction area (m2/kg) 433 342 –

standards. These regulations and standards are currently in a state

of flux. In some cable constructions, a PVC sheath is used over FEP
insulation, preferably with a low-smoke low-flame-spread PVC
formulation.
Some polymer blend formulations said to be suitable for plenum were
presented in 1999 by Brown (Alcan) [35] (Table 9).
Formulations A, B, and C are said to be useful starting point formula-
tions. These results suggest a synergism of the AOM and ZS.
Chlorinated PVC has also been proposed as a useful component in
plenum wiring formulations.

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

232 E. D. WEIL ET AL.

A more extensive discussion by Griffin (2000) of the use of the

ethylene–acrylate–carbon monoxide copolymers (DuPont’s ELVALOY
HP series, especially ECR-742 and ECR HP-441) presents data showing
that these resin modifiers used in PVC formulations can reduce smoke
without sacrifice of strength, elongation, flex modulus, or brittle
point [36]. Plenum cable applications are suggested.

Coated Textile Applications

Flame retardant coated fabrics often have a two-layer vinyl coating,

the inner layer being plasticized with a phosphate (triaryl or alkyl
diphenyl) plus a phthalate ester, and sometimes a chloroparaffin
secondary plasticizer. The outer layer is often plasticized with a
combination of a phosphate plus a non-fugitive polymeric (oligomeric)
ester plasticizer. Additional components may include antimony oxide,
zinc borate, or ATH. A thin acrylic topcoat may also be applied. Roofing
webs consisting of fabric coated on both sides with plasticized PVC,
where the plasticizers must be selected for non-volatility and compat-
ibility with bituminous roofing materials, are flame retarded with
antimony oxide.

Vinyl Flooring

Vinyl sheet flooring usually has two vinyl layers on a fibrous backing,
the lower layer being plasticized usually with a phosphate (triaryl or
alkyl diphenyl) plus butyl benzyl phthalate. The top (wear layer) usually
has a low level of flammable plasticizer so that it does not need a flame
retardant phosphate. Vinyl tile flooring usually does not need a flame
retardant because of the usually high filler level (calcium carbonate
and/or clay) and low level of plasticizer (such as butyl benzyl phthalate).
An acrylic or urethane topcoat is sometimes used but may be somewhat
adverse to flame retardancy.

PVC from a Safety and Environmental Point of View

Misleadingly, PVC has been accused of producing particularly toxic

smoke. It is quite well established that carbon monoxide is the main
killer, and that the toxicity of fire atmospheres is determined almost
exclusively by carbon monoxide. The smoke toxic potency of HCl is of
the same order as that of carbon monoxide. Moreover, hydrogen chloride

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

Flame and Smoke Retardants in Vinyl Chloride Polymers 233

is rather unique amongst major combustion products in that its

concentration decays in a fire as it reacts or is absorbed by many
surfaces. In room corner tests (Factory Mutual), the obscuration caused
by PVC was less than comparative wood panels. A summary of these
relationships has been published by Hirschler [2].
Polyvinyl chloride, in common with other halogenated materials,
has been under environmental attack for decades. The objections to
PVC and other halogenated products are summarized at great length
by an author connected to Greenpeace, an environmental activist
organization [37]. The production of PVC is alleged to release toxic
by-products. The stability of PVC to biodegradation, while a virtue
for a building material (in common with concrete, stone, brick, metal,
and glass), does pose a disposal question. Recycling is certainly
possible and is done to some extent [38]. Landfill disposal is possible
in the United States where there is ample landfill capacity but is less
acceptable in Europe or Japan where there are fewer suitable areas.
Incineration has been controversial because of the formation of
polychlorinated dibenzodioxins and dibenzofurans. There is a very
large body of toxicological literature on these paradoxical compounds,
certain isomers of which are extraordinarily toxic to some animal
species, although the only acute toxic symptom upon high exposure in
humans is a skin eruption called ‘chloracne.’ However, incineration in
modern government-permitted incinerator–scrubber installations has
been found to produce little or no dioxins [39]. Disposal by burning
in smelters and cement kilns is also an option if it is adequately
monitored.
Since PVC has favorable properties from an ignitability, flame spread,
and ease of extinguishment point of view, it must be recognized
that PVC is less likely to be a contributor to fire than many other
plastics. Less well known is the fact that the heat release characteris-
tic of unplasticized PVC is one of the lowest of all combustible
materials [2,22]. Of course, the addition of a conventional phthalate
plasticizer will raise the peak rate of heat release, but as discussed
above, much less flammable plasticizers are used where fire behavior is
important.

CONCLUSIONS

Few plastics have had as thorough a study of environmental

impact, and increasing production and use of PVC can be shown to be
surprisingly benign from a resource and sustainability standpoint [40].

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

234 E. D. WEIL ET AL.

German cities which banned its use in construction have for the most
part returned to its use. Green organizations continue to agitate against
PVC and halogenated products in general, largely based on obsolete
information regarding incineration and emissions, but the industry has
had some success in educating the public and government regarding the
safety of PVC. The objectionable cadmium stabilizers have been phased
out, and lead stabilizers which have caused some concern are being
gradually replaced.
Frequently updated data resources in support of PVC are available
on the Internet [38,40]. PVC in wire and cable has held its position
versus non-halogen alternatives except in situations where smoke and
combustion product corrosivity are dominant considerations, or where
‘green’ marketing strategies prevail. Large new manufacturing facilities
for PVC in the US are being planned [41]. New PVC facilities are also
being built or planned in Europe and Asia. Efforts are being made by
the vinyl industry, particularly in Europe where the challenge is most
intense, to lower the usage of lead-based stabilizers and to develop better
means for recycling of PVC [42]. These incompletely solved problems
have not prevented growth in the usage of PVC [43].

REFERENCES

1. Nass, L.I. and Heiberger, C.A. (1997). Encyclopedia of PVC, 2nd edn, Marcel
Dekker, New York.
2. Hirschler, M. (2005). Flammability and Fire Performance, In: Wilkes, C.E.,
Summers, J.W. and Daniels, C.A. (eds), PVC Handbook, Chapter 13,
pp. 419–482, Carl Hanser Verlag, Munich.
3. Paul, D.H. (1993). Flame Retardants and Smoke Suppressants for Flexible
Vinyl Compounds, J. Vinyl Technol., 15(3): 153–158.
4. Weil, E.D. and Lewin, M. (2000). Synergists, Adjuvants and Antagonists
in Flame Retardant Systems, In: Grand, A. and Wilkie, C. (eds), Fire
Retardancy of Polymeric Materials, pp. 116–137, Marcel Dekker, Inc.,
New York.
5. Jakupca, M.R., Harr, M.E. and Jennings, T. (2000). Improved Chlorinated
Paraffin Secondary Plasticizer Compositions, In: Annual Tech. Conf.,
ANTEC Conf. Proceedings, Vol. 3, pp. 3083–3086.
6. Chen, T. (Huber Corp.) (2003). Comparison of Ground vs. Precipitated Fine
Alumina Trihydrate for Flame Retardant Wire and Cable Applications,
In: 52nd International Wire & Cable Symposium/Focus, Philadelphia,
Nov. 17–20.
7. Thomas, N.L. and Harvey, R.J. (1999). Formulating Rigid PVC to Optimize
Flame Retardancy and Smoke Suppression, Polymers & Polymer Composites,
7(8): 545–553.

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

Flame and Smoke Retardants in Vinyl Chloride Polymers 235

8. Mathis, T.C. and Morgan, A.W. (to Monsanto) (1975). US Patent 3,869,420.
9. Briggs, C.C., Hollingbery, L.A., Day, R.C. and Gilbert, M. (1997).
Optimizing Fire Properties of Plasticized Poly(vinyl chloride) Compounds,
Plastics, Rubber and Composites Processing and Applications, 26(2):
66–77.
10. Wickson, E.J. (1993). Handbook of Polyvinyl Chloride Formulating, John
Wiley & Sons, Inc., New York.
11. Walker, J.K. (2001). Influence of Molybdates on Char Formation and Smoke
Suppression in PVC, In: Presented at Additives 2001, Hilton Head, SC,
March 18–21.
12. Innes, J. and Innes, A. (2004). Smoke Suppression in PVC Systems,
In: Vinyltec 2004 (SPE Conference), Iselin, NJ, Oct. 11–13.
13. Li, B. and Wang, J. (1997). Cone Calorimetric Study of Flame Retardance
and Smoke Emission of PVC, J. Fire Sci., 15(5): 341–357.
14. Li, B. (2002). A Study of the Thermal Decomposition and Smoke
Suppression of Poly(vinyl chloride) Treated with Metal Oxides using a
Cone Calorimeter at a High Incident Heat Flux, Polymer Degradation and
Stability, 78(2): 349–356.
15. McRowe, A.W. and Kroenke, W.J. (to B.F. Goodrich Co.) (1977). US Patent
4,053,453.
16. Starnes, Jr., W.H., Pike, R.D., Adams, C.W., Bunge, S.D., Kang, Y.M.,
Kim, A.S. and Kim, J.H. (1998). Smoke Suppression of PVC by Reductive
Crosslinking, In: Additives ’98 Conference, Orlando, FL, Feb.
17. McKee, D.W. (1986). Borate Treatment of Carbon Fibers and Carbon-Carbon
Composites for Improved Oxidation Resistance, Carbon, 24(6): 737–741.
18. Cusack, P., Cross, M. and Hornsby, P. (2002). Environmentally-friendly
Tin-based Fire Retardants, Flame Retardants 2002, London, Feb. 5–6,
83–88.
19. Thomas, N.L. (2003). Zinc Compounds as Flame Retardants and Smoke
Suppressants for Rigid PVC, Plastics, Rubber and Composites, 32(8–9):
413–419.
20. Herbert, M.J. (1996). Flame and Smoke Suppressants for PVC, British
Plastics and Rubber, June, 26–30.
21. Schartel, B., Kunze, R., Neubert, D. and Tidjani, A. (2002). ZnS as Fire
Retardant in Plasticized PVC, Polymer International, 51(3): 213–222.
22. Innes, J.D. (1996). Interaction of Smoke Suppressants with Other FR
Polymer System Components, In: Addcon ’96 Conference Proceedings,
Brussels, Paper 14.
23. Weil, E.D. (2004). Flame Retardants – Health, Safety and Environmental
Aspects, In: Encyclopedia of Polymer Science and Technology, 3rd edn,
John Wiley & Sons, Inc., NY.
24. Moy, P. (2004). Flame Retardant Options for Vinyl Applications, In: Paper
given at Vinyltec Conference, Iselin, NJ.
25. Duke, A.J. (1978). The Significance of Isomerism and Complexity
of Composition on the Performance of Triaryl Phosphate Plasticizers
in PVC, Chimia, 32(12): 457–463.

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015

236 E. D. WEIL ET AL.

26. Green, J. (1992). Phosphate Ester Plasticizers, In: Edenbaum, J. (ed.),

Plastic Additives and Modifiers Handbook, pp. 448–459, New York,
Van Nostrand Reinhold.
27. Hamilton, J.P. (1972). Modern Plastics, Oct. 1972, 86–90.
28. Shankwalkar, S.G. and Cruz, C. (1994). Thermal Degradation and Weight
Loss Characteristics of Commercial Phosphate Esters, Ind. Eng. Chem.,
Res., 33(3): 740–743.
29. Linsky, L.A., Andries, J.C., Ouellette, D., Buono, J.A. and Tao, T. (to Teknor
Apex) (1999). US Patent 5,886,072.
30. Moy, P. (1996). FR Characteristics of Phosphate Ester Plasticizers with
Antimony Oxide, In: Paper at SPE ANTEC Meeting, Toronto, ON, May.
31. www.specialchem4polymers.com.
32. MAGSHIELD in PVC, Martin Marietta Product Literature, Feb. 1999.
33. Coaker, A.W. (2003). Fire and Flame Retardants for PVC, J. Vinyl and
Additive Technology, 9(3): 108–115.
34. Kroushi, P.W. (to Cooper Industries) (1993). US Patent 5,227,417.
35. Brown, S. (1999). Trends and Developments in Flame Retardants for
Cables, IEEE Colloquium on Developments in Fire Performance Cables for
Energy, Ref. No. 1999/074, pp. 3/1–3/17.
36. Griffin, E.R. (2000). High-Molecular-Weight Flexibilizers in Low-Smoke
Flame-Retardant PVC Compounds, J. Vinyl & Additive Tech., 6(4): 187–191.
37. Thornton, J. (2000). Pandora’s Poison, MIT Press, Cambridge, MA.
38. http://www.vinylfacts.com/science/recycle/recycle_fact.html.
39. Deriziotis, P. and Themelis, N.J. (2003). Substance and Perceptions
of Environmental Impacts of Dioxin Emissions, In: Proceedings of the
11th Annual North American Waste to Energy Conference, Tampa, FL,
pp. 225–230.
40. http://www.ping.be/chlorophiles/en/en_pvc-lca.html.
41. Sim, P.H. (2004). Shin-Etsu to Build $1-billion Vinyls Complex on US Gulf,
Chemical Week, Dec. 15, 8.
42. http://www.vinyl2010.org.
43. Anon., Plastics Additives & Compounding, May/June 2005, 34–37.

Downloaded from jfs.sagepub.com at UNIV OF PITTSBURGH on March 14, 2015