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New Approaches to Halogen Free Polyolefin Flame Retardant Wire and Cable
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 LOES Form Number 311-01001
New Approaches to Halogen Free Polyolefin
Flame Retardant Wire and Cable Compounds
Jeffrey M. Cogen, Jinder Jow, Thomas S. Lin, and Paul D. Whaley
The Dow Chemical Company
Somerset, NJ, USA
(732)-271-7929 jmcogen@dow.com
Abstract
A two-tiered approach has been utilized to develop improved
halogen free flame retardant (HFFR) wire and cable compounds.
The first tier entails utilization of new advanced polymers and
materials as a foundation for improved compound properties. The
second tier is based on new HFFR technologies that provide
unique product capabilities. This combination of advanced
materials and new HFFR technologies provides compounds
having unique balance of processability, flame retardance, and
physical and mechanical properties. New developments in
polyolefin resins, intumescent technology, and synthetic nano-
material are presented in this paper illustrating improved
performances obtained for HFFR wire and cable compounds.
Keywords
Halogen free flame retardant; polyolefin; intumescent; filler;
nanoclay; nanocomposite; aluminum trihydroxide (ATH);
magnesium hydroxide.
1. Introduction
Wires and cables used in enclosed spaces usually must possess
flame retardant properties. A significant fraction of flame
retardant (FR) materials used in cables is halogen free for lower
smoke, toxicity, and corrosivity. Flame retardant polyolefins offer
an excellent, cost-effective balance of properties for halogen free
flame retardant (HFFR) applications. Formulation of polyolefins
to achieve flame retardance requires high levels of additives.
Because the additives tend to negatively impact the mechanical,
physical, and rheological properties of the polymer, development
of high quality HFFR polyolefin compounds requires a smart
manipulation of additive and polymer technology.
A two-tiered approach has been utilized to develop improved
halogen free flame retardant (HFFR) wire and cable compounds.
The first tier entails utilization of new advanced polymers and
materials as a foundation for improved compound properties. The
second tier is based on new HFFR technologies that provide
unique product capabilities. This combination of advanced
materials and new HFFR technologies provides compounds
having unique balance of processability, flame retardance, and
physical and mechanical properties.
2. Results and Discussion
2.1 Resin Technology
Ethylene vinyl-acetate copolymer (EVA) historically has been the
most widely used base resin in HFFR for wire and cable
applications. With the significant recent advances in polyolefin
process and catalyst technology, a broad range of polyolefins now
can be used, alone or as blends, to extend the range of
performance versus that of conventional compounds. The Dow
Chemical Company has available for new product development
both conventional and new proprietary polyolefins made using the
full range of available processes. These proprietary polyolefins
include UNIVAL™ High Density Polyethylene Resins;
DOWLEX* Polyethylene Resins; ATTANE* Ultra Low-Density
Linear Polyethylene Copolymer; AFFINITY* Polyolefin
Plastomers; ELITE* Enhanced Polyethylene Resins;
PRIMACOR* Copolymers; AMPLIFY* Functional Polymers;
EASY FLOW™ HP-LDPE Replacement LLDPE Resins;
TUFLIN™ High Strength LLDPE Resins; FLEXOMER™
VLDPE Resins for Polymer Modification; UNIPOL™
Polyethylene Resins; polypropylene homopolymers, impact
copolymers, and random copolymers; IMPPAX™ Polypropylene
Resins; CEFOR™ butene copolymers; and INSPIRE*
Performance Polymers. Early access to a steady stream of new
polymers helps bring FR grades to the marketplace as quickly as
possible.
Advanced polyolefin resins are used as building blocks for
halogen free FR compounds that possess a unique balance of
properties, including high tear strength, excellent tensile
properties, and advantaged rheological characteristics. These
properties are achieved while maintaining a high level of flame
retardance and flexibility, good low temperature properties, and
dielectric properties that are better than those observed in
conventional HFFR materials.
Results with a new polyolefin are highlighted below. The
advanced new polymer is found to be capable of carrying high
levels of filler without significant loss of physical, mechanical,
and rheological properties. With an unusual thermomechanical
profile for a polymer with high filler acceptance, this
thermoplastic resin also offers performance advantages under
thermal load when compared to alternative non-crosslinked
polyolefins.
The new polyolefin was compounded with 50% by weight of
aluminum tridydroxide (ATH), representative of levels used in a
range of high volume applications. This compound was compared
to a control sample consisting of 50% ATH in an EVA copolymer
(containing 18% vinyl acetate by weight).
*Trademark of The Dow Chemical Company
 LOES Form Number 311-01001

Thermomechanical analysis (TMA) was conducted using a force

of 0.05 Newtons at a heating rate of 5°C/minute. As indicated in 10000
Figure 1, the new polyolefin offers a higher temperature resistance EVA
than EVA, without the need for crosslinking, as indicated by a 20- EVA-ATH
30°C offset in probe penetration rate. This effect is even more New Polyolefin-ATH
dramatically illustrated by the 90°C hot deformation data shown
New Polyolefin

Viscosity (Pa-s)
in Figure 2. The new polymer with ATH had 0% deformation
whereas the EVA sample with ATH had 100% deformation. The
new polyolefin also retains its original mechanical and rheological 1000
properties very well when it contains filler. This is illustrated in
Figure 2, which shows the change in these properties for the
polymers containing 50% ATH relative to the polymers without
any ATH. Figure 3 shows the capillary rheology data, where it
can be seen that the filler has far less of a detrimental effect on the
rheology of the new polymer compared to that of the EVA.
100
100 1000

100% Shear rate (S-1)

90% EVA-ATH
Probe penetration

80%
70% New Poyolefin-
Figure 3. Capillary rheology data at 175°C.
60% ATH

50% In addition to maintaining excellent tensile strength and

40% elongation on a percentage basis as shown in Figure 2, the values
30% are outstanding on an absolute basis for the new polymer with
20% 50% ATH, as shown in Table 1. Thus, the new polyolefin offers a
unique combination of low viscosity, low hot deformation, and
10%
good tensile strength and elongation.
0%
30 50 70 90 110 130 150 170 The new polymer is useful as a filler masterbatch carrier resin, as
a blend component for highly filled systems, or as a base resin for
Temperature °C HFFR formulations.
Table 1. Tensile strength and elongation of
Figure 1. Thermomechanical analysis (0.05 N, extruded tape. Each contains 50% by wt. of ATH.
5°C/min.) of samples containing 50% by wt. ATH. New Polyolefin-
EVA-ATH ATH
Tensile strength psi (MPa) 1900 (13) 2100 (14)
Elongation % 600 700
120
100
80
2.2 Novel Intumescents
60
40 New intumescent systems offer additional latitude in development
20 of HFFR compounds, particularly for insulation applications,
0 EVA-ATH
where performance attributes have traditionally limited use of
intumescents in wire and cable applications. New halogen free
Hot Deformation

New Polyolefin-ATH
Increase* (%)
@ 90°C (%)

Tensile Strength

compounds based on this new intumescent FR technology offer

Viscosity

Elongation Loss*
Loss* (%)

lower density, better processability, flame retardance, and

(%)

electrical properties when compared with traditional metal

*Change relative to hydroxide filled systems.
polymer without ATH
The majority of current halogen-free flame retardant compounds
for wire and cable are based on metal hydroxides, which require
Figure 2. Hot deformation and filler acceptance of high loadings in the range of 50 to 70% to achieve good flame
polymers containing 50% by wt. of ATH. Viscosity retardance. With such high filler loading, electrical properties and
is based on data at 175°C. processability of such products suffer. It has been shown that the
nanocomposite technology can reduce the required loading level
of metal hydroxides, leading to some improvements in properties
[1-2]. However, there is a need for additional improvements in
these properties for certain high value HFFR applications.
 LOES Form Number 311-01001

Intumescent flame retardant technology has been known to offer before water
good flame retardance for many years [3-4]. However, these 3.60 immersion

Dielectric Constant at 1 MHz

systems tend to pick up a significant amount of water under wet or 3.40 after water
humid conditions, resulting in loss of electrical properties [5]. The immersion
3.20
new intumescent technology offers excellent dielectrical
3.00
properties before and after water immersion when compared with
metal hydroxide and conventional intumescent FR systems. 2.80
2.60
The compositions listed in Table 2 are polyolefin compositions
with three different flame retardant systems at loading levels 2.40
needed to achieve an UL-94 V0 rating at a thickness of 125 mil 2.20
(3.2 mm). As expected, both the new and conventional 2.00
intumescent compounds have lower density than the metal Metal Hydroxide Conventional New
hydroxide-filled compound. Both intumescent compounds also Intumescent Intumescent
have better processability than the metal hydroxide-containing
compound, as shown in Figure 4. Figures 5 and 6 show dielectric
constants and dissipation factors of these three compounds Figure 5. Dielectric constant before and after 24-
measured at 1 MHz and room temperature, before and after one hour water immersion at 40°C.
day water immersion at 40°C. The data clearly show that the new
intumescent FR compound has better electrical performance than 0.1000
before water

Dissipation Factor at 1 MHz

metal hydroxide-filled and conventional intumescent FR immersion
compounds. This new halogen-free FR technology offers an after water immersion
alternative to metal hydroxide-filled technology for applications 0.0100
requiring better dielectric properties and processability. It
achieves this while also providing lower density and excellent
flame retardance. 0.0010

Table 2. Compositions and densities of the UL-94 0.0001

V0 rated intumescent compounds and a metal Metal Hydroxide Conventional New Intumescent
hydroxide-based control. Intumescent

Meta l Conventiona l New

Compositiions (% by weight) Hydroxide Intumescent Intumescent Figure 6. Dissipation Factor before and after 24-
Polyolefins 35 65 65 hour water immersion at 40°C.
Metal hydroxide 65
Conventional intumescent 35
New intumescent 35
Density 1.49 1.08 1.05 2.3 Nanocomposites
UL-94 rating at 125 mil (3.2 mm) V-0 V-0 V-0
The benefits of nanocomposites in FR compounds have been well
documented in the literature, and advantages for wire and cable
applications have also been established [1-2]. Improved flame
10000 retardance imparted by nano-materials can be utilized to lower the
Metal Hydroxide overall level of flame retardant in the polymer compound while
New Intumescent maintaining a given level of flame resistance. This approach
Conventional Intumescent
enables materials having improved physical and mechanical
Viscosity (Pa-s)

properties compared to non-nanocomposite compounds.

1000
Alternatively, the improved flame retardance can be utilized to
develop formulations having a higher level of flame retardance
without significant degradation of physical and mechanical
properties when compared to a non-nanocomposite compound
having the same total FR additive level. These approaches are
illustrated schematically in Figure 7.
100
100 1000 Most nanocomposites in the polyolefins industry are based on
Shear Rate (1/s) organically modified natural montmorillonite clay. Despite the
excellent properties of nanocomposites based on natural
Figure 4. Capillary rheology at 190°C showing montmorillonite, tradeoffs exist, including geographically limited
improvement in viscosity of intumescent availability, variable purity, and color. In addition, cost has
compounds versus the control. limited the growth of nanocomposites. To circumvent these
limitations, a synthetic nano-material has been developed. The
new material is white, highly pure, and reproducible in
composition. Because it is synthetic, it can be manufactured
anywhere.
 LOES Form Number 311-01001

In an accompanying paper [2], detailed results are presented 350

showing that the new synthetic nano-material provides flame and Montmorillonite
mechanical properties comparable to natural montmorillonite, 300 New nano-material

Heat Release Rate (KW/m2)

without the above-mentioned tradeoffs commonly associated with 250
Control
nanocomposites made from natural mined nano-materials. Some
key data are summarized in Table 3, comparing EVA-based 200
nancomposites made using montmorillonite and the new nano-
150
material to a non-nanocomposite control.
100

Nanocomposite 50
Flame performance

Nanocomposite 0
0 100 200 300 400 500 600
Time (sec)
Traditional
Nanocomposite
Compound Figure 9. Heat release rate data from cone
calorimeter (heat flux = 35 kW/m2).
Physical and mechanical properties
Table 3. Data on nanocomposites versus a control
Figure 7. Approaches to utilize benefits of formulation.
nanocomposites. 50% Mg(OH)2 + 5%
50% Mg(OH)2 + 5%
Synthetic nano- 55% Mg(OH)2
Montmorillonite
material
UL-94 vertical burn rating V-0 V-0 None
Cone calorimetry curves showing the smoke and heat release rates Cone calorimetry
2
are shown in Figures 8 and 9. The data indicate a large Peak heat release rate (kW/m )
-1
199 176 316
Peak smoke release rate (s ) 2.7 2.6 4.5
improvement in the nanocomposites versus the control. The Tensile strength psi (MPa) 1800 (12) 1800 (12) 1800 (12)
reduction in peak heat release rate is 37% and 48% for the Elongation at break (%) 250 300 275
nanocomposites made using the montmorillonite and new nano-
material, respectively, versus the control. The reduction in peak 3. Putting it all Together
smoke release rate is about 40% for the nanocomposites, versus The technologies discussed above are part of the growing toolbox
the control. available to develop advantaged HFFR compounds for wire and
Tensile strengths and elongations are comparable for all three cable applications. Specific examples of new compounds that use
compounds (Table 3). If additional Mg(OH)2 is added to the these and/or related technologies are highlighted below.
control to bring the flame performance on par with the
nanocomposites, the tensile strength and elongation will be
significantly reduced. 3.1 Flexible Easy Processing Compound
While providing comparable performance to montmorillonite, the Viscosity of polymer compounds decreases as the processing
new nano-material solves the tradeoffs commonly associated with temperature increases. For applications requiring excellent
nanocomposites made from natural mined nano-materials, processability and high flame retardance (>35 LOI), conventional
including geographically limited availability, variable purity, and compounds based on aluminum trihydroxide (ATH) are not
color. suitable due to the decomposition of ATH, which occurs at a
significant rate above about 175°C. Flexibility is also an important
5.0 attribute in many wire and cable applications. Table 4 shows data
4.5 Montmorillonite
for a new flexible compound, Exp #1, that can be processed at
Rate of Smoke Release (1/s)

4.0 New nano-material temperatures up to about 220°C. (Note that the data in Table 4
3.5
Control represent non-oriented plaque samples. Elongation is lower than
3.0
would be observed with oriented samples such as extruded tapes
or cable coatings, but is useful for comparative purposes.) Data on
2.5
the leading industry compound for this application are also
2.0
included. The new compound achieves a reduction in flexural
1.5 modulus of 58%, indicating much better flexibility, while
1.0 maintaining other key properties. As shown if Figure 10, Exp #1
0.5 has similar shear rheological performance to the leading
0.0 compound.
0 100 200 300 400 500 600
Time (sec)

3.2 General Purpose HFFR Compound

Table 5 highlights properties of two new HFFR compounds
Figure 8. Smoke release rate data from cone
targeted for global general-purpose markets where cost-
calorimeter (heat flux = 35 kW/m2). effectiveness is especially critical. The products offer an
outstanding balance of properties not normally found in
compounds having 37 – 42 LOI. These include tear strength
 LOES Form Number 311-01001

above 7 N/mm, low temperature brittleness lower than –40°C, Table 5. Two new HFFR compounds targeted for
excellent flexibility, low smoke, and good aesthetic properties. global general-purpose market.
Cable trials have verified these properties and also indicated good
Compound Properties Method Typical values
processability and unusually low scratch whitening.
Exp #2 Exp #3
Density g/cc 1.49 1.49
ASTM
Flexural modulus, psi (Mpa) 39000 (270) 50000 (350)
D790
Table 4. Data obtained from plaques comparing Tensile strength, psi (MPa)
ASTM
1800 (12) 1700 (12)
the new compound (Exp #1) to a leading D638
ASTM
compound as a control. Elongation (%)
D638
200 200

Leading Exp #1 LOI (%)

ASTM
37 42
compound D2863
(control) UL-94 vertical burn (3.2 mm) UL-94 V-0 V-0
Tensile Strength psi (MPa) 2000 (14) 2200 (15) ASTM
LTB (-40°C) Pass Pass
D746
Elongation (%) 150 150
ASTM Not
Shore D hardness 45
Durometer, Shore A 95 90 D2240 measured
Dow
Durometer, Shore D 58 54 Hot deformation, 90°C (%)
Method
3 1

LOI (% O2) 36 37 Tear strength, lbs/inch ASTM

44 (7.7) 41 (7.2)
(N/mm) D470
Tear lbf/in (N/mm) 28 (4.9) 28 (4.9) ASTM
Dissipation factor (%) 0.01 0.01
Flexural Modulus psi (MPa) 40,000 17,000 D150
ASTM
Dielectric constant 3.4 3.4
Maximum extrusion temp. °C 220 220 D150
Smoke density flaming mode ASTM Not
99
Ds max (2.6 mm) E662 measured
Smoke density non-flaming ASTM
156 168
mode Ds max (2.6 mm) E662
Not
Corrosivity of gas (pH) IEC 332-2 5.9
measured
Corrosivity of gas Not
IEC 332-3 21.5
(conductivity micro S/cm) measured
10000 Odor during extrusion None None
Appearance White White
Max extrusion Temp°C 175 175
Viscostiy (Pa-s)

1000 4. Conclusions
A combination of advanced polymer technology and advanced
flame retardant technology provides an ideal approach to the
development of superior non-halogenated flame retardant
100 compounds for wire and cable applications.
Control Novel polyolefins based on new catalyst technology provide
polymers that extend the performance range beyond that of
Exp #1 previously available materials.
10 New intumescent approaches mitigate performance drawbacks
10 100 1000 10000 that have heretofore hindered the exploitation of this promising
class of flame retardants in wire and cable applications.
Shear rate (s-1) Novel synthetic nano-materials offer the ability to make
nanocomposites that are free of the tradeoffs normally associated
with nanocomposites based on natural nanoclays.
Figure 10. Capillary rheology at 220°C, showing
Drawing from these and other technologies in the growing
comparable viscosity for the new flexible technology toolbox, new compounds are available to address
compound and the leading compound (control). unmet needs in the marketplace. In addition, these tools provide
the capability to solve a range of material challenges to bring
improved, more cost-effective solutions to the wire and cable
compounds market.
 LOES Form Number 311-01001
5. Acknowledgements
The authors would like to thank the following Dow colleagues for
their helpful suggestions: John Klier, Scott Wasserman, and
Anteneh Worku. In addition, the authors would like to
acknowledge Alexander Morgan and Juan Garcés of Dow for
their contributions to the nanocomposite work discussed in this
paper. That work is presented in an accompanying IWCS/Focus
paper.
6. References
[1] G. Beyer, “Nanocomposites as a New Class of Flame
Retardant,” Proceedings of the 51st International Wire
and Cable Symposium, 584-588 (2002).
[2] J. Cogen, T. Lin, A. Morgan, and J. Garcés, “Novel
Synthetic Nanocomposite Materials and Their
Application in Polyolefin-Based Wire and Cable
Compounds,” accompanying paper in Proceedings of
the 52nd International Wire and Cable Symposium
(2003).
[3] H. Horacek and S. Pieh, “The Importance of
Intumescent Systems for Fire Protection of Plastic
Materials,” Polym Int 49, 1106-1114 (2000).
[4] G. Camino and R. Delobel, “Intumescence,” in Fire
Retardancy of Polymeric Materials by A.F. Grand and
C.A. Wilkie, Marcel Decker, pp 217-245, 2000.
[5] T. Futterer, H-D. Nägerl, K. Götzmann, V. Mans, and E.
Tortosa, “Halogen Free Flame Retardant Polyolefines
Technology: Studies on Various Synergistic Systems
Based on APP,” Proceedings of the 2002 Flame
Retardants Conference, London, England, February 5-6,
2002.
 LOES Form Number 311-01001
Authors
Dr. Jeffrey M. Cogen is a Research Leader in Dow’s Wire and
Cable Compounds group. He has a B.A. in Chemistry from
Cornell University and a Ph.D. in Organic Chemistry from the
University of California, Berkeley. His technical experience
includes design, synthesis, testing, and formulating of additives
for polyolefins. He has several years of wire and cable compound
development experience, for both power and communication
cable. Present interests include flame retardant polyolefin
compounds and reactive extrusion, and he is currently the Science
Partner for Dow's Flame Retardant Wire and Cable Compounds
business. He has authored or coauthored 15 technical articles and
is an inventor on 22 issued and pending patents.
Dr. Jinder Jow is a research leader in Dow's Wire and Cable
Compounds group. He has a BS from National Taiwan University
and a Ph.D. from Michigan State University, both in Chemical
Engineering. His technical expertise is in product development
and flame retardance and electrical degradtion in polymers. He
holds more than 8 patents, and has authored or co-authored more
than 20 publications and conference papers. His current focus is
development of new product techology for new markets.
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Dr. Thomas S. Lin is a senior research specialist in Dow’s Wire
and Cable Compounds group. He has a B.S. in Chemical
Engineering from University of Washington and a Ph.D. in
Chemical Engineering from Cornell University. His technical
background includes product development, pilot plant operations,
and manufacturing scale-up in both petroleum and chemical
industries. His present research areas include polymer flame
retardance, polymer stabilization, and nanocomposites for wire
and cable applications. He has five publications and two issued
patents. He has been involved in several industry standard
committees in telecom and automotive wire and cable areas. He
is presently an active member of SAE Cable Task Force. He is a
member of American Institute of Chemical Engineers, Society of
Plastics Engineers, and Society of Automotive Engineers.
Dr. Paul D. Whaley is a research specialist in Dow’s Wire and
Cable Compounds group. He has a B. S. in Chemical Engineering
from the University of Toledo and a Ph.D. in Polymer Science
and Engineering from the University of Massachusetts at
Amherst. His technical background includes polyethylene product
development and manufacturing scale-up during assignments with
Univation Technologies. Presently, his research area focuses on
halogen-free flame retardant product formulation. He is the author
of eight technical articles and is an inventor on two issued and
pending patents. He is a member of the Society of Plastics
Engineers.