MATERIALS FOR USE IN FIRE RISK AREAS

M E Slevin

Introduction

In the cable industry the traditional materials for use in fire risk areas have been halogenated polymers
predominantly based on polyvinylchloride. However a major change in requirements for fire retardant
materials began in the 1970's.

The driving force for change came as a result of major fires associated with cables in the private and
public sectors resulting in loss of life. Most notable examples are the fires in the Falklands war in 1982
and Kings Cross in 1987. In addition major damage to installation and equipment by evolved acidic gases
was also incurred such as was found in fires for example in the Illinois Bell Telephone exchange, USA
in 1988.

PVC when burnt emits large quantities of dense black smoke and acid gas, and in addition to the
debilitating effect of smoke and toxic fume inhalation, obscuration of fire safety exits delays or prevents
escape. Improved PVC formulations producing less smoke and acid gas have been developed but still do
not satisfy required emission levels. The demand therefore has been for materials to replace PVC which
do not give off smoke and toxic fumes and do not contain halogens. The materials need to have the
following characteristics:-

a) fire retardant and zero halogen

b) low emission of smoke, toxic fumes and acid gases during combustion
c) similar mechanical and electrical properties to PVC
d) acceptable processability
e) low additional cost

Extensive development work conducted by Compounders and Cable Companies have largely satisfied the
-
requirements of a) d) above, but the requirement for low additional cost is still being pursued.

To date development of alternative materials has concentrated on polyolefins as the base resin being the
lowest cost alternativeto PVC resin. Polyolefin materials are however flammable and require the addition
of high levels of fire retardant additives to inhibit burning.

Fire Chemistry
Materials bum due to the evolution of hydrocarbon combustible gases. The process is exothermic occurs
in the gas phase and is sustained by a free radical chemical reaction in the presence of oxygen. In
simplified form the reactions are:-

-
H.+ O2 OH.+ 0:
OH.+ CO H.+ CO2 exothermic chain propagation reaction
4

There are several methods by which to inhibit the burning process:-

M E Slevin AEI Compounds,A Division of the General Electric Company p.1.c.

' 1996 The Institutionof ElectricalEngineers.

rinted and publishedby the IEE. Savoy Place, London WCZR OBL, UK. 111
a) Addition of Halogens

Halogens such as chloride inhibit frce propagation by interfering in the reaction described above.
Hydrogen halides (HX)formed during burning 'scavenge' the H. and OH. radical thus terminating
the propagation reaction. The reactions occur in the gaseous phase.

OH.+ HX -.H,O +X
H. + HX-,H2 +X
Antimony oxides are often used with halogenated FR systems, providing synergistic action.

b) CharFormers
Formation of a solid char is-an effective barrier to fire propagation, and although polymer type
and hydrate loading contribute to char strength, other specific additives are used. Phosphorus
compounds and boron containing materials form effective glassy chars which protect the substrate
from the flame source. Foaming or intumescing the char layer provides further insulation. Other
glass forming additives are also used. Many of these additives tend to show poor moisture
resistance,are expensive and are only used to a limited extent in cable compounds.

c) Addition of Inorganic Fire Retardants

The majority of inorganic fire retardants are based on metal hydrates such as aluminium trihydrate
and magnesium hydroxide. They function by edothermic decomposition liberating water both
cooling and diluting the flame. In addition the oxide formed following decomposition is non
combustible :-

Aluminium hydrates decompose at = 180°C and Magnesium hydroxide at = 250°C.

Cable Compounds

The majority of zero halogen flame retardant compounds developed for the cable industry are based on
aluminium trihydrate (ATH) loaded into polyolefin materials typically at 60% weight fraction. ATH is
used primarily due to its low relative cost compared to other zero halogen additives such as Magnesium
Hydroxide which is 2-3 times more expensive than ATH. The cost of ATH can be however compared
to calcium carbonate used in PVC fomulations which is 6 times cheaper than ATH.

The polyolefin materials used are based on ethylene vinyl acetates (EVA),ethylene ethyl acrylate (EEA)
and very low density polyethylenes (VLDPE) with the new metallocene catalysed polyethylenes being
investigated. Thermoplastic Low Smoke and Fume ( LSF) materials are used mainly for sheathing of
cables and crosslinked LSF materials used for insulation or where specifications require the material to
be crosslinked. The addition of the high loadings of ATH into polyolefin materials can however create
performance deficiencies in a number of areas.

a) Mechanical Performance

Low tensile strength, elongation at break and tear strength values are obtained when poor
compatibility between polymer and filler occurs.

1I2
 The elevated temperature mechanical performance of LSF materials has been found in some cases
to be poor. In particular, a weakening in tear strength at elevated temperature can result in poor
resistance to crack propagation initiated for example by mechanical damage during cable
installation.

Improvements in mechanical performance have been achieved by:-

- Modification of the surface chemistry of the inorganic ATH filler by attachment of organk
additives to the filler surface improving compatibility with the organic polymer network.
- Chemical coupling between the organic coated filler and polymer chain.
- Seleaion of polymers with high softening points gives increased elwated temperature
performance. In this regard the trend is from low VA polyethylene copolymers to very
low density polyethylenes. Optimum characteristics can be obtained by blending polymer
types.

Figs 1 and 2 show the variation in tensile and tear strength at elevated temperature for two LSF
compounds. Tests were generally to BSEN 60811 and BS 6469. The improvement in
performance is achieved by optimised chemical coupling and particularly by polymer selection,
with higher softening point polymers giving improved elevated temperature performance.

b) Wet Electrical Resistance

The insulation resistance of ATH filled polymers can deteriorate significantly in water immersed
conditions. The purity of the ATH used, particularly with regard to sodium ion content is
important, but other factors such as polymer type and surface chemistry of the ATH have
significant effect.

Improved ATH fillers are now available ‘electrical grades’ with low levels of residual sodium ions
giving improved wet electrical performance. Additionally the surface coupling or treatment by
organic additives confers a hydrophobic surface further improving water resistance. Long term
wet electrical testing has been conducted on both thermoplastic and silane crosslinked LSF
materials including energised cables. Fig 3 illustrate the variation in wet electrical properties for
cores insulated with LSF materials. It can be seen that significant differences in wet electrical
stability can be found for different LSF materials. Polymer type can have an effect, but significant
improvements in long term performance can be achieved by chemical modification of the filler
surface. It can be seen that differing LSF materials show differing performance with regard to
water absorption.

c) Processability

Low smoke LSF materials are generally much more viscous than PVC compounds requiring
modified extrusion equipment, particularly so as ATH filled polymers must be processed at 170°C
to prevent decomposition compared to extrusion temperatures of 210°C for PVC. Low
compression extrusion scrolls generating low shear characteristics coupled with larger powered
extruder motors are generally required for LSF materials.

Improvements in processability have been obtained by appropriateselection of polymer lubrication

systems, but the trend to higher mechanical performance does lead to increased viscosity materials.
When lower fire performance standards can be tolerated, then the lower filler levels used result
in improved processability. Fig 4 compares the rheological characteristics of a number of LSF
materials and illustrates the increased melt viscosition of LSF materials compared to PVC.
Crosslinking of LSF Materials

Crosslinking of LSF materials whilst conferring increased operating temperatures can also improve fire
performance characteristics. Crosslinking inhibits polymer flow improving char formation during buming.
Both peroxide and silane crosslinked systems are used with irradiation crosslinking occurring to a lesser
degree. Peroxide crosslinking is mainly used for rubber type cables with silane crosslinking used for both
rubber and plastic cable applications. Table I shows the properties of two silane crosslinkable LSF
materials. Compound A has been used for 16 years in a wide range of cable designs, both as insulation
and sheath and can be compared to the nwer grade compound B which shows improved fire re-tardaucy.

Compounding Technique

Crucial to the attainment of good overall property performance is the compounding efficiency of the
polymer formulation. Many of the LSF materials produced today rely on dynamic chemical coupling in
the compounder. The many variables in formulation such as filler moisture content and PH can have
significant effects on the properties of the material due to interference in the chemical coupling reactions
described earlier. Control of compounding conditions such as melt temperature and mix technique are
essential for reproducibility of formulation characteristics.

Future h d s

There are many types of LSF materials available which compfy with specification requirements such as
those in BS 6724 but which differ in performance as described earlier. Additionally specific property
requirements such as UV resistance, flexibility, abrasion and high temperature rating (125°C for
automotive) are found in many other cable applications requiring specialised LSF formulations.

For building wire and communication cable where material cost is particularly important, much effort is
being conducted to produce lower cost ISF materials by reduction or replacement of filler where lower
fire Performance can be accepted.

Future trends are therefore for there to be a wider range of LSF materials available satisfying specific
specification or property requirements at the lowest cost.

I Table 1 1

Hot Set 2ON/cm 200"

OxygenIndex 96 I 28 36 ASTM D2863

Temperature Index "C 280 320 NES 715 I

1/4
I I

I Fig 1 Tensile strength v Temp.

I

1 J
r

Fig 2 Tear strength v Temp.

Fig 3 Variation in insulation resistance for 35"l core

immersed in water at 20%

--......- .-._.._-

r
--B-LSFll
-X-LSF 2
4C-LSF 3 I
i

Fig 4 Rheological Characteristics

Shear rate (11s)