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EPDM formulations for electric wires and cables

Article · January 2001

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EPDM compositions
aluminum hy-
droxide
mechanical properties

electrical properties
EPDM formulations were developed
with both carbon black and alumi-
num hydroxide as fillers. Mechanical
and electrical properties were eval-
uated with the purpose to find out
those compositions which would
meet the Brazilian Association for
Technical Standards, ABNT, require-
ments as for their use in wires and
cables. As expected carbon black
has a negative effect and its pre-
sence should be restricted to less
than 22 phr if these materials are to
be used in the range of medium
voltages (up to 15 kV).
EPDM Rezepturen fuÈr Elektro-
draÈhte und Kabel
EPDM Rezepturen
Aluminium Hy-
droxid
mechanische Eigenschaften

elektrische Eigenschaften
EPDM Rezepturen mit Ruû und Alu-
minium Hydroxid als FuÈllstoffe wur-
den mit dem Ziel entwickelt, die
mechanischen und elektrischen Ei-
genschaften den Anforderungen der
Brazilianischen Vereinigung fuÈr
Technische Normen (ABTN) anzu-
passen und eine Verwendung bei
der Isolation vor DraÈhten und Ka-
beln zu finden. Wie erwartet hat Ruû
einen negativen Effekt. Daher sollte
die Ruûkonzentration auf 22 phr be-
schraÈnkt werden, wenn diese Mate-
rialien im mittleren Spannungsbe-
reich (bis zu 15 kV) eingesetzt wer-
den.
56
ELASTOMERE UND KUNSTSTOFFE
ELASTOMERS AND PLASTICS
EPDM Formulations for Electric
Wires and Cables
C. Canaud, M. Antonio Sens, L. L. Yuan Visconte,
R. C. Reis Nunes, Rio de Janeiro (Brazil)
Ethylene-propylene-diene copolymers
(EPDM) constitute a class of terpolymers
whose rheological and physical proper-
ties like flow patterns or the degree of
crystallinity, respectively, are strongly af-
fected by the polymer composition, that
is, the relative amounts of the comono-
mers involved [1].
Due to the saturated chain backbone,
EPDM can be employed in different for-
mulations, each one adequate to a spe-
cific application, in which characteristics
such as resistances to ozone, heat,
moisture and intemperism, flexibility to
low temperatures, wide range of tensile
strength and excellent electrical insula-
tion properties are required [1 ± 3]. These
properties, being particularly important in
the electrical sector, have stimulated an
increasing utilization of EPDM-based
compositions in medium and high volt-
age insulating cables and wires, in cables
electric terminals and in polymeric insula-
tors [4 ± 7]. In the past this market has
been supplied mostly by PVC, mainly be-
cause of its low flammability, low cost,
good performance and processability.
However PVC has been considered a
matter of concern by the ambientalists
due to the presence in its compositions
of chlorine and heavy metal based stabi-
lizers which are liberated or can liberate
toxic gases during combustion [8].
Nevertheless, the addition of aluminum
hydroxide has rendered these effects
weaker.
Despite these steps forward concern-
ing the use of PVC, EPDM rubbers have
increased their participation in the market
of wires and cables since they present
several advantages, compared to PVC.
Among them a low sensitivity to UV radia-
tion, low toxicity and corrosion power and
KGK Kautschuk Gummi Kunststoffe 54. Jahrgang, Nr. 1-2/2001
a remarkable chemical resistance have to
be mentioned. Yet, EPDM is highly flam-
mable and needs to be protected with
high percentages of a flame retarder. In
general, amounts as high as 100 phr
are necessary to impart EPDM a good
level of flame retardancy. So, although re-
latively expensive when compared to
other rubbers, EPDM is able to accept
high amounts of fillers which, at the
end, helps to achieve cheaper final pro-
ducts. Thus the combination of charac-
teristics such as processability, low
cost, low weight and excellent insulating
properties has turned polymeric materials
into those the most used in electrical ap-
plications [9].
Wire and cables insulation is expected
to avoid the contact among the conduct-
ing elements, where electricity goes
through, from other elements, providing
the conductors also with an appropriate
mechanical support. The insulator is ap-
plied on the conductor as thin layers and
one must point out that these small
amounts employed are submitted to ele-
vated electrical demands and thus these
materials have to be looked at with spe-
cial care as to their mechanical proper-
ties.
The heat overload in the conductors
resulting, for example, from imperfect
connections, is a potential source of igni-
tion, which may put the whole electrical
installation in danger, since the structural
element present in the cable coating, that
is, the polymer, is a highly inflammable
material. Thus, the use of polymeric ma-
terials in electrical applications requires a
special precaution with regard to fire pos-
sibility. Both material and the shape of the
electrical appliances must be carefuly se-
lected as to guarantee that they will not
 EPDM Formulations for Electric Wires and Cables
Table 1. Formulations used in EPDM compositionsa
Ingredient 0 1
EPDM 100 100
Carbon black ± N330 0 22
ATHb 0 150
Zinc oxide 5 5
Stearic acid 1 1
Sulfur 1.5 1.5
Paraffinic oil 25 25
MBTc 0.5 0.5
TMTDd 1.0 1.0
a
In phr
b
Aluminum hydroxide; 2 types were used: with and without surface treatment
c
Mercaptobemzothiazole
d
Tetramethylthiuram dissulfide
burst into fire or facilitate fire propagation
when in operation conditions, due to ma-
terial failure or exposition to an external
flame [10 ± 13].
Amongst flame retarders, aluminum
hydroxide (ATH) is the most used pre-
sently. The main reason for the increasing
usage of this material can be credited to
its cost-benefit relationship [14, 15]. The
main advantages of ATH over other flame
retaders are the low cost and reduced
toxicity, and the fact that ATH can act si-
multaneously as both flame retardant and
smoke suppressor agents. It does not lib-
erate toxic or corrosive substances in
high temperature conditions [14,16 ± 18].
As a semi-reinforcing filler, ATH does
not significantly increase mechanical re-
sistance when incorporated in a poly-
meric material and, thus, a few superficial
treatments with silanes and titanates
have been carried out with the purpose
to improve the reinforcing character of
ATH [14].
In this work, EPDM formulations were
developed by incorporating carbon black
(N330) and ATH as fillers, in different
amounts. Mechanical as well as electrical
tests were performed to determine the
applicability of these compositions as in-
sulating coatings for electrical wires and
cables.
Experimental
The recipes used to prepare EPDM for-
mulations are presented in Table 1.
The compositions were prepared in a
roll mill at 30 8C and vulcanized in a hot
press at 160 8C. Volumetric and superfi-
cial resistivities were determined on a
610 C Solid State Electrometer. The rela-
tive permissivity and the dissipation factor
KGK Kautschuk Gummi Kunststoffe 54. Jahrgang, Nr. 1-2/2001
180 phr [19, 20]. Thus, in this work the
compositions studied had a minimum
2 3 4
of 150 and a maximum of 180 phr of
100 100 100 ATH. As the fillers used, N330 and
15 7.5 0
160 170 180 ATH, have different densities, the
5 5 5 amounts of each filler in the mixes were
1 1 1 calculated on a volume basis, with the
1.5 1.5 1.5
25 25 25
precaution to keep constant the total vol-
0.5 0.5 0.5 ume of fillers at 74:4 cm3 .
1.0 1.0 1.0 Table 2 presents the values of stress
and strain at break for the compositions
investigated.
Comparing to pure gum, the semi-re-
inforcing character of ATH can be ob-
served since the presence of this filler im-
proves the stress at break. However, this
measurements were carried out on a
improvement is more significative when
Waynekerr Precision Inductance Analy-
N330 is added in larger quantities. Appar-
ser 3245, using a Tettex AG guard ring
ently, the surface treatment had a positive
capacitor. The dielectric resistance was
effect only in the composition having ATH
determined by using a AC Dielectric
as the only filler.
Test Set model 7100-10, as the voltage
According to ABNT, the compositions
source, and a Peak Voltmeter VAH 792
150/22, 160/15, 160/15* and 170/7.5
to measure the breakdown voltage. All
meet the requirements of stress at break
experiments followed ASTM methods
for materials to be applied in electrical
and the results were compared to pure
wire and cables. Considering strain at
gum.
break, all compositions could be used.
From the values of modulus, the for-
Results and discussion mulations were all superior to pure
gum, specially those in which ATH had
EPDM formulations were obtained by
been treated with silane (Table 3). How-
partially replacing carbon black by ATH,
ever, for each type of ATH, the variation
superficially trated or not with silane,
in the amount of filler did not have
with the purpose of determining the effect
much influence on this property.
of this substitution on mechanical and
Hardness is a measure of the resis-
electrical properties. Since these compo-
tance of a material to local deformations
sitions were thought to be used in electri-
[21 ± 23] and depends, among other fac-
cal applications, they had to be adjusted
tors, on the amount of filler, the number of
as to fulfill the Brazilian Association for
crosslinks and may also be related to
Technical Standards (ABNT) together
modulus. As already observed for this
with the requirement to present charac-
last property, hardness is positively influ-
teristics of flame retardancy. According
enced by filler incorporation, as shown in
to the literature, anti-flame characteristics
Table 3, since all compositions presented
are met when ATH is incorporated in
hadness values higher than pure gum.
quantities in the range of 150 to
This property, however, was not affected
Table 2. Stress and strain at break for EPDM compositions
ATH/N330 (phr) Stress at break (MPa) Strain at break (%)
0/0 1.65 178
150/22* 9.1 329
150/22 11.4 417
160/15* 11.2 360
160/15 13.8 404
170/7.5* 8.7 424
170/7.5 10.8 503
180/0* 8.0 393
180/0 6.6 427
ABNT requirements > 10 > 300
*
ATH with silane
57
 EPDM Formulations for Electric Wires and Cables

Table 3. Modulus at 100 %, hardness and tear strength of EPDM compositions Electric resistivity measures how resis-
tant a material is to the the passage of
ATH/N330 phr Modulus at 100 % Hardness Shore A Tear strength
MPa kN/m current through its surface or its volume,
thus avoiding the escaping currents, re-
0/0 1.3 45 6.32
150/22 2.9 71.5 31.09 sponsible for its heating and capacity
150/22* 4.8 73 38.16 loss as insulator, for a given application.
160/15 4.4 73.5 29.16 In this regard, resistivity data must be
160/15* 5.2 73 35.83
170/7.5 3.6 71.5 23.92
as high as possible.
170/7.5* 5.1 72.5 35.17 Minimum values are found for the com-
180/0 3.7 71 22.14 position 120/45 and these values ap-
180/0* 5.3 72 30.07 proach that for pure gum, as the amount
*
ATH treated with silane of N330 is reduced. It can also be ob-
served that the silane treatment did not
bring any significant effect. Probably,
neither by the amount nor the type of tension necessary to produce a dielectric the expected positive effects resulting
ATH. rupture. It is expressed in volts divided by of a better matrix-filler adhesion, caused
In applying polymeric materials as in- the material thickness [9, 26, 29] and data by the surface treatment, have been
sulating coatings for electrical wires and for this property are shown in Table 4. counterbalanced by the presence of the
cables, tear resistance is a very important From the analysis of the Table, a drastic polar groups in the coupling agent,
property. Low tear resistances may in- reduction in the dielectric rigidity, which is thus leading to a reduction in the volu-
crease the chances of microfissures related to the application of elevated elec- metric resistivity. The superficial resistivity,
which are responsable for the appearing tric fields, is observed for the composition for its turn, takes into account factors as
of electric discharges and, in conse- 120/45. The others, excepting composi- impurities and moisture.
quence, of electric ruptures and insula- tion 150/22, had an increase in the rigidity The dielectric constant, also shown in
tion loss [24]. The behavior of tear resis- as more ATH was incorporated. This can Table 4, measures the ability a material
tance for the compositions investigated be due to differences in shape presented has to store charge [30, 31] and the abso-
can also be seen in Table 3. by the different fillers. Carbon black par- lute values for this property should be as
From this Table, all compositions pre- ticles are agglomerated and, although the low as possible for a material be consid-
sented tear resistance values superior average size of its particles (3ÿ10 m) is ered as an insulator. Again, the values of
to pure gum for both types of ATH, but smaller than ATH particles (10ÿ6 m) the dielectric constant approach the one ob-
even higher for the silane-treated series. tendency for agglomeration results in lar- tained for pure gum, as the amount of
Large amounts of ATH were, neverthe- ger volumes containing occluded voids. ATH increases. The effect of the silane
less, deleterious to this property. Thus, These voids can promote current es- treatment is not significative for the
in the search for better mechanical prop- capes, exposing the installation to elec- same reasons as discussed before.
erties, higher incorporations of carbon tric discharges and leading to a rapid per- The dissipation factor is said to be the
black were tried by preparing composi- foration of the polymeric composition. ratio between the current lost by the insu-
tions with filler ratios equal to 120/45 Data also show a slightly superior behav- lator (escape current) and the amount of
and 140/30, but as will be seen later, iour for the compositions with non-trea- charge that crosses the conductor, when
these formulations were not suitable for ted ATH, since the treatment imparts a tension is applied, this quantity being
electric applications. an induced polarity to this filler. expressed in percentage. The dissipation
The electrical properties evaluated in Values of superficial and volumetric re- factor is then a measure of the dielectric
this work were superficial and volumetric sistivities are also presented in Table 4. loss that occurs due to the dielectric re-
resistivities, dielectric constant, dielectric
rigidity and dissipation factor, which are
the most important properties in qualify- Table 4. Dielectric properties of EPDM compositions
ing a material as an electric insulator ATH/N330 phr Dielectric rigidity Log Superficial Log Volumetric Log Dielectric
[25, 26]. kV/mm resistivity X resistivity Xm constant
Electrical properties can be divided in 0/0 27.4 16.19 16.52 0.37
two groups. In general, in the first one 120/45 1.2 7.65 7.94 2.74
the resistance of a polymer to a low inten- 120/45* 1.8 8.00 7.93 2.78
sity electric field is evaluated and in this 140/30 9.6 15.41 14.71 0.94
140/30* 11.0 15.17 14.67 0.95
group properties like dielectric constant 150/22 25.8 14.18 14.80 0.59
and dissipation factor are included. The 150/22* 24.7 15.35 14.76 0.60
second group is constituted by those 160/15 21.8 14.37 14.81 0.65
160/15* 20.5 14.44 14.76 0.66
properties which are important in more in- 170/7.5 26.6 15.80 15.09 0.59
tense electric fields, such as electric dis- 170/7.5* 25.2 16.04 14.91 0.60
charge and rupture [9, 27, 28]. 180/0 32.9 15.84 14.85 0.54
The dielectric rigidity of an insulating 180/0* 32.7 15.63 14.73 0.57
material can be defined as the maximum *
ATH treated with silane

58 KGK Kautschuk Gummi Kunststoffe 54. Jahrgang, Nr. 1-2/2001

 EPDM Formulations for Electric Wires and Cables
Figure 1. Influence of filler composition on dissipation factor
laxation, in consequence of a delay in the
dipole orientation with the applied field.
The variation of the dissipation factor
with frequency is due to a reduction of
the dielectric constant as the frequency
increases and is directly related to a high-
er or lower easiness the dipoles have to
align themselves with the alternate field
[32]. So, larger molecules or agglomer-
ates experience more difficulty to orient
themselves in the alternate field fre-
quency and become out of phase in rela-
tion to it, causing a reduction in polariza-
tion and in dielectric constant.
From Figure 1, the most intense dissi-
pation is observed when 45 phr of N330
are used, due to the conducting charac-
teristics of this filler, and decreasing val-
ues are found as the amount of N330
is also decreased. Slightly superior values
KGK Kautschuk Gummi Kunststoffe 54. Jahrgang, Nr. 1-2/2001
Figure 2. Variation of dissipation factor with frequency in EPDM
compositions containing silane treated ATH
are also observed for the compositions
with silane treated ATH.
In order to verify the possibility of moist-
ure absorption, which in big amounts
would rise questions concerning the va-
lidity of the aforementioned electric anal-
ysis, the dissipation factor was measured
at different frequencies. A crescent linear
relationship would be an indication of
moisture absorption.
Figures 2 and 3 present the dissipation
factor behavior as a function of frequency
for the different compositions and show a
small variation of this property as fre-
quency increases, followed by a ten-
dency to level off, suggesting that there
was not enough moisture absorption as
to disguise the results obtained.
From the results, it can be concluded
that, due to its conductive nature, the
Figure 3. Variation
of dissipation fac-
tor with frequency
in EPDM compo-
sitions containing
untreated ATH
presence of N330 leads to a reduction in
the dielectric properties (for use as insu-
lators), when the formulations are com-
pared to pure gum, and that this effect
is more drastic when this filler is present
in higher amounts. This can be related to
the formation of a conductive filler net-
work above a percolation limit [33].
According to ABNT, to be useful as
electric insulators, the material must
have the following characteristics:
* A dielectric constant varying between
2.0 and 4.0, at room temperature
and 1 kHz frequency;
* Concerning the dielectric rigidity, the
material must resist to 22 kV tension,
to be used in voltages up to 15 kV,
and to 30 kV, to be used in voltages
up to 20 kV;
* The loss factor must not exceed 2 %,
at room temperature.
Thus, analysing the results and consid-
ering only the electric aspects, the com-
positions 150/22 and 170/7.5 are suita-
ble for application in medium voltages
(up to 15 kV) and 180/0 for high voltages
(up to 20 kV) wires and cables. However,
when mechanical resistances are also
considered, only compositions 150/22
and 170/7.5, both containing untreated
ATH, meet the ABNT requirements.
References
[1] N.P. Cheremisinoff. In: ªHandbook of Polymer
Science and Technologyº, N.P. Cheremisinoff,
ed, Marcel Dekker, New York, 1989, Chapter 2.
[2] Y. Schowob, Caoutchoucs & Plastiques 733
(1994) 72.
59
 EPDM Formulations for Electric Wires and Cables
[3] L.K. Arnold. In: ªIntroduction to Plasticsº, G. Al-
len, ed, Unwin Ltd, London, (1969).
[4] R.D. Allen. In: ªHandbook of Polymer Science
and Technologyº, N.P. Cheremisinoff, ed, Marcel
Dekker, New York, 1989, Volume 2.
[5] J. Gossot, Caoutchoucs & Plastiques 752
(1996) 65.
[6] J.W.M. Noordmeer, Rubber World 216 (1997)
16.
[7] R.C. Keller and D.A. White, Rubber World 206
(1992) 20.
[8] N. BuÈthe, U. Giese, R.H. Schuster, G. WuÈnsch,
Kautsch. Gummi Kunstst. 53 (2000) 42.
[9] V. Shah. In: ªHandbook of Plastics Testing Tech-
nologyº, V. Shah, ed, John Wiley & Sons, New
York, 1984, Chapter 4.
[10] W. Becker, H. Rupprecht and H. Troitzsch. In:
ªInternational Plastics Flammability Handbook:
Principles-Regulations-Testings and Approvalº,
J. Troitzsch, ed, Hanser Publishers, New York,
1990, Chapter 8.
[11] W. Kauffmann, F.H. Prager and H.W. Schiffer. In:
ªInternational Plastics Flammability Handbook:
Principles-Regulations-Testings and Approvalº,
J. Troitzsch, ed, Hanser Publishers, New York,
1990, Chapter 11.
[12] J. Storey, Plastiques Modernes et Elastomeres
48 (1996) 29.
[13] M.M. Hirschler, Polymer Degradation and Sta-
bility 54 (1996) 333.
[14] I. Sobolev and E.A. Waycheshim. In: ªHandbook
of Fillers for Plasticsº, H.S. Katz, ed, Van Nos-
trand Reinhold, New York, 1987, Chapter 5.
[15] J.B. Gallo, M.Sc. Thesis, Centro de CieÃncias Ex-
atas e de Tecnologia, UFSCar, SaÄo Carlos, Brazil
(1996).
[16] L. Mascia, Thermoplastics: Materials Engineering,
Elsevier Science Publisher Ltd, New York, 1989.
[17] J. Green, Rapra Reviews Report 4 (1991) 3.
[18] P. Hodge, Rapra Reviews Report 52 (1996) 3.
[19] F.W. Keeley and U.I. Vaidya, Electrical Elasto-
mers, Du Pont, 6.
[20] K. Shen, P. Thyot, J.M. Lopez-Cuesta and R.
Delobel, Plastiques Modernes et Elastomeres
48 (1996) 24.
[21] R.P. Sheldon. In: ªComposite Polymeric Materi-
alsº, R.P. Sheldos, ed, Applied Science Publish-
ers, New York, 1982, Chapter 3.
[22] V. Shah. In: ªHandbook of Plastics Testing Tech-
nologyº, V. Shah, ed, John Wiley & Sons, New
York, 1984, Chapter 2.
[23] R.B. Seymor. In: ªProperties of Solidsº, R. B.
Seymor, ed, ASM International, USA, 1987.
60
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[24] M. Zanim and J.A. Giacometti, PolõÂmeros:
CieÃncia e Tecnologia (1997) 30.
[25] C.C. Ku and R. Liepinss. In: ªElectrical Proper-
ties of Polymers: Chemical Principlesº, Hanser
Publishers, New York, 1987.
[26] D.W. Krevelen, Properties of Polymers, Their
Correlation with Chemical Structure, form Addi-
tive Groups Contribuitions, Elsevier Science
Publishers, New York, 1990.
[27] Quabin Wire & Cable (1996) 1.
[28] V.R. Sickar, B.A. Briskman and I.G. Bukanov,
Polymer Science 39 (1997) 720.
[29] C.C. Ku and R. Liepins, Dielectric breakdown of
polymer. In: C.H. Verlog, editor, Electrical Prop-
erties of Polymers: Chemical Principles, Hanser
Publishers, New York, 1989.
[30] C.J. Hilado, Testing to flammability. In: C.J. Hi-
lado, editor, Flammability Handbook for Plastics,
Technomic Publishing, Westport, 1974.
[31] C.C. Ku and R. Liepins, Dielectric constant of
polymers. In: C.H. Verlog, editor, Electrical Prop-
erties of Polymers; Chemical Principles, Hanser
Publishers, New York, 1987.
[32] C.C. Ku and R. Liepins, Tangent of dielectric loss
angle of polymers. In: C.H. Verlog, editor, Elec-
trical Properties of Polymers: Chemical Princi-
ples, Hanser Publishers, New York, 1987.
[33] M. Gerspacher, ªCarbon black reinforcementº,
presented at WARC ± Worldwide Amazon Rub-
ber Conference, Manaus, Brazil (1999).
The authors
Cristine Canaud concluded her M. Sc. Thesis on this
subject. Marcio Antonio Sens, Materials Department,
Centro de Pesquisas de Energia EleÂtrica ± CEPEL,
Cidade UniversitaÂria. Regina CeÂlia Reis Nunes and
Leila LeÂa Yuan Visconte are Associate Professors
at the Instituto de MacromoleÂculas Professora Eloisa
Mano, Universidade Federal do Rio de Janeiro
Corresponding author
Regina CeÂlia Reis Nunes
Centro de Tecnnologia
Bloco I
Cidade UniversitaÂria
Ilha do FundaÄo
C.P. 68525
CEP 21945-970 Rio de Janeiro
RJ, Brasil
KGK Kautschuk Gummi Kunststoffe 54. Jahrgang, Nr. 1-2/2001