Technology+Development+for Low Smoke
Technology+Development+for Low Smoke
Reddy P V*
An attempt was made to develop technology for low-smoke flame-retardant cable and compound with
elimination of toxic chemicals in the formulation. The extrusion trials using twin screw extruder and
cable coating with single screw extruder were successful. Results of the evaluation of the cable and
compound suggest that the composition seems to be satisfactory. However, large-scale production
could not be taken due to the actual technoeconomic viability of the commercialization. This study
paved the way for DSIR-sponsored project for commercial exploitation under PATSER scheme.
During the early part of the development period,       More recently, in what has developed into the
the emphasis was on flame-retardant and to reduce      largest market for flame-retardant chemicals,
flame propagation of cables. More recently,            flame-retardancy is engineered into polymers
interest has centered in cables which evolve           and, thus, is a result of the inherent properties of
reduced levels of smoke and toxic fumes.               the materials.
Polyvinylchloride (PVC) is being used abundantly       The market for flame-retardant PVC compounds is
for insulation and sheathing of electric cables.       growing, as these plastics compete for increasing
In case of a fire, normal PVC cables burn with         applications in residential buildings, industrial
difficulty, but in certain conditions; for example,    buildings, public buildings, automobiles, aircraft,
when cables are installed vertically, PVC will burn    upholstery and clothing. Other significant
and can cause fire to spread rapidly. Polyvinyl        markets include electrical insulation and military
chloride is inherently flame-retardant and hence its   equipment. The requirements for flame-retardancy
compositions represent one of the largest markets      are becoming more rigorous as these markets
for flame-retardant applications. In unplasticized     are penetrated, test methods have become more
form, PVC is flame-retardant due to its high           realistic and sophisticated and awareness of the
chlorine content (approximately 57 %). When PVC        inherent danger in using flammable materials is
is compounded with diaromatic ester plasticizers       increasing. This awareness has been accentuated
and other modifiers, the resultant compositions        by the total destruction, by fire, of buildings that
will usually be combustible. One kilogram of soft      were supposedly fire proof due to combustible
PVC when subjected to fire will emit 360 g of HCl      contents, furnishings and decorations.
gas, which when dissolved in water results in 1L
of concentrated smoking hydrochloric acid. The         1.2 Development/Design Criteria for Flame-
flammability of plasticized PVC can be controlled          Retardant Power Cables
by the use of suitable additives. In order to impart
flame-retardance with low-smoke characteristics,       In the event of a fire involving cable runs, the
and to minimize toxic gas formation during             protective cable sheath of a multicore cable will
burning of PVC compound, additives involving           be the first component exposed to the flames/or
elements like chlorine, phosphorus, antimony,          to the radiant heat flux. Thus, the design criteria
alloys, inorganic compounds, coordination as           for the development of cable sheath or jacket in
well as several organometallic compounds are           fire must consider in optimizing the fire/pyrolysis
used. Low-melting sulphate glass has also been         behavior of materials. In general, it can be said
identified as an effective fire-and smoke-retarding    that the task of the polymer expert is to develop
additive for PVC [1].                                  new materials which are transformed from ‘Easy
                                                       to Burn’ stage to ‘Difficult to Burn’ stage. New
1.1 History of the Flame-Retardant                     materials should also perform well in reducing
    Chemicals Industry                                 the smoke generation and acid generation
                                                       significantly. In addition, the cable insulating and
Fire causes a huge amount of human suffering, as       sheath materials should have high fire resistance
well as personal and business financial loss. For      and maintain electrical integrity under conditions
nearly a century, with mixed success, attempts         of electrical stress and exposure to flame so that
have been made to remove the fire hazard from          essential services are maintained.
items encountered in everyday life. Man-made
materials, in particular, have been the subject of     1.3 Fundamental Aspects of
intense research concerning their behavior in fires.       Burning of Polymers
Initial applications were aimed at reducing the
combustibility of fabrics or substrates by coating     Polymeric materials (hard or soft) are linear or cross-
them with chemicals. Later, the industry began         linked macromolecular organic materials which do
to increase the fire-resistance of materials by        not burn easily. However, their flammability arises
incorporating an additive or reactive compound.        from the fact that they are unstable at temperatures
The Journal of CPRI, Vol. 7, No. 1, March 2011                                                           81
of ≥200°C, providing a range of small volatile         place during the standard processing operations to
organic compounds, which are highly flammable.         render the product useless. Under the effect of heat
These products of thermal degradation evolving         and light/UV radiation, polyvinyl chloride looses
large amounts of heat cause further degradation,       its HCl molecule continuously, soon leading to
rapidly leading to serious fire. Most polymers         a chain segment of polyunsaturation, resulting in
decompose at temperatures between 220 and              the loss of mechanical or electrical properties. To
500°C and rapid oxidation may start at approx.         eliminate this effect, certain materials known as
150°C. The presence of oxygen plays a main role        stabilizers must be added. It has been found that
in the decomposition as long as the surface is not     incorporation of stabilizers retards or moderates
flamming. This is because the oxygen depletion         the degradation reaction so that useful processable
in the actual flame is so large that little amount     materials may be obtained.
of oxygen is enough to reach the burning surface.
The decomposition is then almost a thermal             There is a great deal of uncertainty in the
decomposition. Once this situation is reached, it      mechanism of PVC degradation, but certain
is said that fire has developed and combustion is      facts have emerged. Firstly, dehydrochlorination
in progress.                                           occurs at an early stage in the degradation
                                                       process. There is some infrared evidence that as
1.4 Theory of Processing of PVC with                   hydrogen chloride is removed, polyene structures
    Additives                                          are formed. At one time, it was thought that the
                                                       liberated HCl caused autocatalytic liberation
The normally used processing additives for PVC         of further hydrogen chloride, but there is now
are plasticizers, stabilizers, lubricants, fillers,    growing evidence that this is not the case.
etc.
                                                       A second fact that has emerged is that oxygen
1.4.1 Plasticization of PVC                            has an effect on the reaction. It is believed that
                                                       oxygen can cause both chain scission and cross-
PVC is unique in its acceptance of large amounts       linking reaction, while it has also been observed
of plasticizers with a gradual change in physical      that the presence of oxygen accelerates color
properties from rigid solid to soft gel or viscous     formation.
liquid.
                                                       The first physical manifestation of degradation
Method of Plasticization: The plasticizer is           used in the widest sense is a change in the color
incorporated into the PVC resin by means of hot        of PVC. Initially, on heating, water white will
compounding. This process requires an energy           turn, in sequence, pale yellow, orange, brown
input by heating, accompanied by vigorous              and black. Further degradation causes adverse
mixing. At laboratory scale, the plasticizer and       changes in mechanical and electrical properties.
resin powder are mixed in a plasticorder at
150–170°C. The resin–plasticizer blend initially       The choice of a stabilizer, thus, becomes an
offers very little resistance to mixing. A slight      empirical yet systematic process. The following
increase may be noticed as dry blending takes          factors are the most important that must be
place. As the resin-plasticizer blend begins to fuse   considered.
and plasticization occurs on the surface, resistance
to mixing increases rapidly. This is seen by the       1.   The grade of the polymer used.
sudden increase in torque in the plasticorder. Some    2.   The nature of other ingredients present.
of the commonly used plasticizers are phthalates,
phosphates, paraffinic oils, napthenic oils, etc.      3.   The cost of stabilizer required to give
                                                            adequate stabilization for the processing and
1.4.2 Stabilization of PVC                                  anticipated service life of the compound.
                                                       4.   The clarity of the compound required.
At processing temperatures used in practice
(150–200°C), sufficient degradation may take           5.   Toxicity.
82                                                                 The Journal of CPRI, Vol. 7, No. 1, March 2011
6.   The effect on lubrication, printing, heat        a filler with a higher volume cost because more
     sealing and plate-out.                           can be incorporated. To judge the economics of
                                                      a filler simply on its price per unit weight is of
The most important class of stabilizers are the       little merit. For electrical insulation, China clay is
lead compounds, which form lead chloride on           commonly employed, whilst magnesium carbonate
reaction with hydrogen chloride evolved during        and various calcium carbonates are used for
decomposition. They are also good heat stabilizers.   general-purpose work.
Of these materials, basic lead carbonate (2PbCO3·
Pb(OH)2) has been, and probably still is, the         1.4.4 Addition of Lubricants
most important stabilizer for PVC, on which it
confers excellent thermal stability and electrical    In plasticized PVC, the main function of a lubricant
resistivity at temperatures around 160°C. It may      is to prevent sticking of the compound to surfaces
be considered as typical of the lead compounds        of the processing equipment working at high
and has a low weight cost. One disadvantage of        temperature and speeds. This is brought about
lead carbonate is that it may decompose with          by selecting a material of limited compatibility
the evolution of carbon dioxide and water at the      which will thus sweat out during processing to
higher range of processing conditions of above        form a film between the bulk of the compound and
190°C, thus leading to a porous product.              the metal surfaces of the processing equipment.
                                                      Calcium stearate (Ca(C17H35COO)2) has been
For this reason, at higher working temperatures,      used most commonly with non-transparent
tribasic lead sulphate (3PbO·PbSO4·H2O) has been      products, and stearic acid with those that are
found to be a good heat stabilizer. It is in itself   transparent.
very stable to heat and can be heated without
decomposition to temperatures well in excess of       1.4.5 Means of Imparting Flame Resistance
those normally encountered in compounding and               to PVC
fabricating PVC, such as high speed extrusion.
In the absence of any decomposition, it ensures       Most commercial plastics burn fairly easily even
sound products with complete absence of porosity      under moderate conditions. Therefore, it is a
caused by evolution of gases. It gives polymer        common practice to use flame-retardants (FRs)
compounds better electrical insulation property       for improving the fire-resistance performance
than lead carbonate. Its weight cost is somewhat      and reducing the tendency for smoke emission.
higher than that of lead carbonate, but less than     Today, a variety of different FRs are available in
most other stabilizers.                               the market which are often tailor-made for specific
                                                      applications. FRs are compounds that possess
1.4.3 Addition of Fillers                             special structural or chemical features that can
                                                      modify and transform the properties of polymers in
Fillers are commonly employed in opaque PVC           such a way that they retard the flame and emit low
compounds in order to reduce the cost. They may       smoke. Elements such as phosphorus, halogens,
also be employed for technical reasons such as        etc. are used to transform polymers to FRs which
to increase the hardness of a flooring compound,      not only give high performance, but are also
reduce tackiness of highly plasticized compounds,     cost-effective.
improve electrical insulation properties and
improve the heat deformation resistance of            The most common approach that is adopted by
cables.                                               the industries for flame-retardance is the use
                                                      of halogenated flame-retardants. Halogen can
In evaluating the economics of a filler, it is        be added to the system as flame-retardant, but
important to consider the volume of filler that can   are more efficient when incorporated into the
be added before bringing the processing and service   substrate of the polymer as a reactive flame-
properties below that which can be tolerated. Thus,   retardant. However, these retardants develop
in some cases, it may be more economical to use       thick smoke and corrosive gases. The polymers
The Journal of CPRI, Vol. 7, No. 1, March 2011                                                             83
with high amount of inorganic fillers are suitable      trihydrate (ATH). ATH acts as a mineral flame-
for reducing smoke.                                     retardant and smoke suppressant because of its
                                                        thermodynamic properties. Al2O3.3H2O contains
The design of flame resistance into plastics is         34.6 % of water. The retardant is obviously effective
essentially based on empirically gained knowledge.      because of the heat required to decompose the
The role of active smoke-retarders is to change         hydrate and evaporate the water. When exposed
the thermal degradation pattern of PVC and to           to heat, it will absorb about 280 cal/gm before
promote the formation of char. In practical form        liberating water vapor. At 200°C, chemically
(i.e. taking into account economic limitations and      combined water of hydration begins to liberate.
performance characteristics), flame resistance is       This endothermic decomposition absorbs thermal
imparted by the incorporation of halogen-bearing        reactive energy from the flame. The endothermic
compounds, specifically chlorine and bromine,           cooling is believed to favor dehydrogenation
phosphorus-or boron-containing compounds,               reactions and protect char formation. The
and by nitrogenous materials, either singly or          evolution of water not only has a cooling effect
used in combination. Their effectiveness can            but also blankets the flame and acts as a diluent.
be, and frequently is, augmented by auxiliary           The aluminum oxide layer, formed by dehydration,
synergistically acting compounds. Flame-                has an exceptionally high surface area. The high
retardants can be classified into three categories:     surface area of alumina absorbs smoke and
(a) Reactive type : The fire-retardant reacts           flammable molecules, causing a reduction in the
    chemically with the polymer components              amount of carbon dioxide evolved. It has been
    and is combined chemically into the basic           suggested that ATH acts as an electron donor
    polymeric structure.                                to terminate radical reactions, by giving rise to
                                                        relatively unreactive inorganic free radical, which
(b) Additive type : The fire-retardant is               is incapable of initiating further radical reactions.
    physically blended into the base polymer            Other excellent properties include electrical
    prior to conversion to the final product. These     arc/track and corrosion resistance.
    types are usually preferred for thermoplastic
    polymers.                                           1.5.1 Smoke Suppressants
(c) Co-additive type : This includes compounds          Copper oxalate and ammonium molybdates
    which by themselves are ineffective as              provide an effective combination in PVC
    flame-retardants, but in the presence of halogen,   compositions to suppress smoke formation on fire
    phosphorus, nitrogen or boron-containing            without having adverse effects on the properties
    compounds provides synergistically improved         of the polymer composition. These additives are
    flammable characteristics.                          normally used in powder form in amounts of
                                                        about 1–20 phr. These can be easily mixed with
1.5 Metal-Based Flame-Retardants                        PVC in the powder form.
For many years, metal hydroxides have been              Smoke suppression by char formation can be
established to substitute critical organic FR in        achieved by using low-melting sulphate glasses.
applications where the human life is directly           When heated, these systems form a cellular foamed
threatened in a fire. The halogen-and acid-free         char on the surface, which is thermally stable and
character of such substances in combination             protects the underlying polymer from the action of
with halogen-free plastics is promoting and             flames. Low-melting ternary sulphate and modified
pushing the trend to use environmentally benign         sulphate glasses based on transition metals like
products. During combustion, metal hydroxides           copper and nickel reduce the smoke generation
do not evolve toxic or corrosive gases as well as       during burning of the PVC compound.
remarkably suppress the emission of smoke.
                                                        The objective of this work was to develop the
Nowadays, the most widely used acid-free                technology for flame-retardant low-smoke material
and halogen-free flame-retardant is aluminium           for wires and cables for sheathing applications.
84                                                                    The Journal of CPRI, Vol. 7, No. 1, March 2011
                                  Flame-Retardant
Antimony trioxide
                                  additive
                                  Flame-Retardant       3.0 RESULTS AND DISCUSSION
Ammonium molybdate
                                  additive
                                                        PVC formulations, as described above, have
                                  Flame-Retardant
Trihydrated alumina                                     been made and designated as C1, C2, etc. A large
                                  additive
                                                        number of formulations have been studied with
                                  Flame-Retardant       various plasticizers, stabilizers, fillers and flame-
Low-melting sulphate glass
                                  additive
                                                        retardants additives, including sulphate glass.
The Journal of CPRI, Vol. 7, No. 1, March 2011                                                                       85
The study also includes some of the commercially                   the oxygen index values, appreciably decreases
available raw materials like martinal, mica powder,                the smoke density rating values [2,3]. As the
etc. The compositions which have been selected                     concentration increases, thermal stability and
for extrusion trials along with their properties are               to, certain extent, the percent elongation values
listed in Table 3. The flame-retardant properties                  decrease. This decrease in stability and elongation
of PVC compound with variation in sulphate                         has been restored by the use of trioctyltrimellitate
glass (phr) are presented in Table 4.                              (TOTM) plasticizer in place of dioctyl
                                                                   phthalate (DOP) or diisodecyl phthalate (DIDP)
The addition of low-melting sulphate glass to                      plasticizers. The properties obtained from CPRI
PVC composition while marginally increases                         -developed formulations compared with different
TABLE 3
TABLE 4
specifications for FRLS product [4] are given in      3.2 Highlights of the Achievements
Tables 5 and 6.
                                                      (i) Development of low-smoke flame-retardant
                                                          Cables and Compounds.
Note:
                                                      (ii) Attempt to eliminate the toxic chemicals in
(1) The properties obtained are within the
                                                           the formulation of the compound.
    specified limits of BIS.
(2) The thickness of the cable extruded appears       (iii) Extrusion trials using twin screw extruder
    to be less than the required value. This can be         and cable coating with single screw extruder
    adjusted at the time of cable extrusion.                were successful.
                                                TABLE 5
                            SPECIFICATIONS FOR FRLS CABLE COMPOUND
          Properties               Industry Spec.      BIS Spec.           CPRI Results              Aim
Oxygen Index (%)                        30                  29                  29–34                  31
Smoke density (%)                       60                  60                  45–65                40–60
Tensile strength (N/mm2)                12.5               12.5                 10–17                12–14
Elongation (%)                          150                150                 100–180               >150
Thermal stability (min), 200°C          80                  80                  80–90                80–90
Acid generation (%)                     ≤20                ≤20                   ≤20                  ≤20
Volume resistivity (Ω-cm)              1×1013             1×1013                1×1013              1×1013
                                                TABLE 6
                             PROPERTIES OF CABLE SAMPLE EXTRUDED
                     Properties                       Values obtained                Required values
Oxygen index (%)                                           30.5                Min 30
Smoke density (%)                                          56.8                <60
Tensile strength (N/mm2)                                  13.6                 Min 12.5
Elongation (%)                                            171                  Min 150
Thermal stability (min), 200°C                             85                  >80
Acid gas generation (%)                                    14.7                20 % maximum
Shrinkage (%) (150°C for 15 min)                            1.31               4.0 % maximum
Volume resistivity                                          1.03               1 × 1013
Ω-cm, RT × 1015                                             3.04               1 × 1010
    70° C × 1010
High voltage 3 kV, 5 min                                   withstood           To withstand
Insulation thickness (mm)                                   0.853              0.90 mm
The Journal of CPRI, Vol. 7, No. 1, March 2011                                                        87
3.2 Techno-economic Viability of the                      amount of ATH suggests that the processing/
    Commercialization of Results of the                   compounding is by making use of kneader-
    Project and Plans to Commercialize                    type low-compression mixing [5].
[4] Reddy P V, Rajasekhar P, Sridhar S and     [5] Reddy P V. “PVC rubber blends for enhanced
    Jaichand D. “Improved FRLS-PVC compound        flame retardant applications”, CPRI, Tech.
    for Wires and Cables”, Workshopon Power        Report, No. 302, 1996.
    Cables and its Scenario, RTL, Ghaziabad,
    CPRI, July 2002.