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Highly Flexible Halogen Free and Flame Retardant Thermoplastic Cable

Compounds Modified with EVM Polymers

Article · January 2001

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 Highly Flexible Halogen Free and Flame Retardant Thermoplastic Cable
Compounds Modified with EVM Polymers

Manuel La Rosa, Albertus Tankink, Martin Hoch

LANXESS Deutschland GmbH, Technical Rubber Products
Leverkusen, GERMANY
+49-214-3024531 · manuel.larosa@lanxess.com

Abstract
Ethylene vinyl acetate copolymers (EVA or EVM) are well
known for their halogen free character, good oil resistance (high
Vinyl Acetate content) and synergistic effects with many flame
retardants, especially magnesium hydroxide (MDH) and
aluminium hydroxide (ATH). The development of halogen-free
and flame retardant (HFFR) polymeric materials have become an
important and potential trend especially in the construction and
shipbuilding industry. Composite polymer matrices were
characterized with Atomic Force Microscopy (AFM) in order to
understand macromolecular morphology and different levels of
interactions between the different polymers used in this
development. Furthermore, the use of different vinyl acetate (VA)
content polymers, maleic anhydride acid (MA) grafted EVM and
LLDPE in the modification of thermoplastic compounds
contribute to improve different features in developed compounds.
These materials were used aiming an increase of the level of
incorporation of polar inorganic hydroxide fillers - due to
compatibilization effects - as well as retention of tensile strength
and elongation at break after immersion for 4 hours at 70°C in
IRM 902 test oil. Other properties such as retention of properties
after hot air ageing test at 100°C for seven days and tensile
strength tests at -15°C were conducted in order to evaluate their
effect in temperature ageing resistance and low temperature
properties of the developed compounds.
On top of that flame retardant properties such as: Limiting
Oxygen Index (LOI), Heat Release Rate (HRR), carbon monoxide
/carbon dioxide ratio (CO/CO2) and Smoke Density were
evaluated in these compounds. The optimization of a balanced
rheological properties profile: Melt Flow Index (MFI), Melt
Volume rate (MVR) and Mooney Viscosity were considered
during the whole development phase. The importance of keeping
high output rates during compound processing and production
was considered along the whole development, aiming at
composites with adequate properties for the cable industry.
industry only in 2007 the demand largely outpaced the most
optimistic expectations, with more than 169 million dwt
(deadweight tonnage) of new orders which represents nearly 3000
new ships in one year alone, this is double the figure that was
ordered in 2003 [1]. Another area which is positively influencing the
shipbuilding industry are offshore platforms and vessels used for the
oil and gas exploration and production same way the building
construction industry particularly in countries such as China, Turkey
and Spain.
The demand for highly flexible and oil resistant, halogen free flame
retardant (HFFR) cables in these sectors is very high and it is being
enforced by law and regulations demanding more and more
substitution of PVC based cables through polyolefin and other non
halogen containing materials. Compounds based on Linear Low
density Polyethylene (LLDPE), Ethylene Vinyl Acetate (EVA) and
Aluminium trihydroxide (ATH) are extensively used in insulation
and jacketing for cables. To obtain adequate fire retardance, high
loading of approximate 60 wt% of ATH is always needed, which
leads to the deterioration of mechanical and processing properties [2].
Properties such as flexibility and hardness are strongly influenced
by the filler loading of the compounds making cables very stiff and
difficult to handle during installation.
Ethylene vinyl acetate rubbers (EVM) comprise the segment of
EVA copolymers with vinyl acetate content between 40 and 90
wt%. Copolymers with vinyl acetate (VA) content above 80% are
amorphous but have a high glass transition temperature as well as
pronounced thermoplasticity [3]. The chemical structure of Ethylene
vinyl copolymers is described in figure 1:
Ethylene Vinyl Acetate Ethylene Vinyl Acetate Copolymer
H2C CH2 + HC CH2 Ö n m
O O
H3C O H3 C O

Keywords: Ethylene vinyl acetate copolymers, halogen free

flame retardant, HFFR, EVM, EVA, maleic acid grafted EVM,
thermoplastic cables, flexible cables, oil resistance.

Figure 1: Chemical structure of EVM Copolymers.

1. Introduction
The oil, shipbuilding and the construction industries have
experienced a dramatic growth during in recent years; this growth
has been driven mainly by the spectacular economic development of
countries such as India, China and Brazil. For the shipbuilding

International Wire & Cable Symposium 125 Proceedings of the 57th IWCS
The main characteristics and advantages are mentioned as follows: Aidvii Polydimethylsiloxane PDMS Masterbatch and fine Calcium
• Halogen free polymer Carbonate viii (CaCO3) Density = 2,7 g/cm³; Ethylene-Octene
Plastomerix MFI = 10 g/10 min, Density = 0,902 g/cm³.
• Oil, UV and Ozone resistant due to saturated backbone
• Temperature resistant up to 170°C Table 1 Formulations of EVA based thermoplastic cable
• Improved compatibility with polar fillers compounds using different EVM rubbers and MA-g-LLDPE as
compatibilizer.
• Reduction of Smoke density COMPOUNDS CA C1 C2 CB C3 C4
• Better char formation EVM (VA=45 wt %) 9,37 8,42
EVM (VA=80 wt %) 9,37 8,42
• Low heat combustion with high VA content grades EVA (VA=27 wt %) 29,96 20,59 20,59 26,93 18,53 18,53
EOC 3,75 3,75 3,75 3,37 3,37 3,37
The use of rubber materials as modifiers of thermoplastic cable MA-g-LLDPE 3,75 3,75 3,75 3,37 3,37 3,37
compounds has gained considerably importance in recent years. In ATH (BET 3,5 m²/g) 61,80 61,80 61,80 55,55 55,55 55,55
PDMS Masterbatch 0,37 0,37 0,37 0,34 0,33 0,33
fact, plastic-rubber blends possess a unique position in the polymer Stabilisator 0,37 0,37 0,37 0,34 0,33 0,33
blend family because of their thermoplastic elastomeric (TPE) Calcium Carbonate (CaCO3) 10,10 10,10 10,10
nature, meaning some elastomer-like performance properties Total [%] 100,00 100,00 100,00 100,00 100,00 100,00
coupled with plastic-like processing characteristics [4]. Following Density [g/cm³] 1,513 1,522 1,546 1,583 1,592 1,616

this approach we combined low VA EVA with EVM in

thermoplastic compounds to provide certain advantages such as:
Table 2 Formulations of EVA based thermoplastic cable
higher flexibility, lower smoke density of compounds, high
compounds using different rubbers and MA-g-EVM as
Limiting Oxygen Index (LOI) and better oil resistance. We also
compatibilizer.
added Ethylene-Octene copolymers (EOC) with important features
COMPOUNDS CC C5 C6 CD C7 C8
such as: flex-fatigue resistance, lower density, good electrical
EVM (VA=45 wt %) 9,37 8,42
properties, thermal stability and good processability [4], providing an EVM (VA=80 wt %) 9,37 8,42
excellent balance of mechanical and processing properties in 28 wt EVA (VA=27 wt %) 29,96 20,59 20,59 26,93 18,53 18,53
EOC 3,75 3,75 3,75 3,37 3,37 3,37
% VA resin based compounds. All of this was done, aimed to MA-g-EVM (VA= 45 wt %) 3,75 3,75 3,75 3,37 3,37 3,37
overcome disadvantages associated with the necessary high loadings ATH (BET 3,5 m²/g) 61,80 61,80 61,8 55,55 55,55 55,55
of metal hydroxides for producing environmentally friendly cables PDMS Masterbatch 0,37 0,37 0,37 0,34 0,33 0,33
Stabilisator 0,37 0,37 0,37 0,34 0,33 0,33
especially when designing lighter and more compact constructions Calcium Carbonate (CaCO3) 10,10 10,1 10,1
plus higher cable production throughput [5]. Total [%] 100,00 100,00 100,00 100,00 100,00 100,00
Density [g/cm³] 1,520 1,522 1,546 1,589 1,592 1,616
In order to improve the compatibility with the low VA content resin
maleic-acid-grafted LLDPE (MA-g-LLDPE) and EVM (MA-g-
2.2 Preparation of Compounds
EVM) were tested. Maleic Acid grafted polyolefins are widely used
The ingredients were compounded in an internal mixer (GK 1,5E
to improve the compatibility of polar fillers in rather non polar
from Werner & Pfleiderer). The compounding procedure in the
polymer matrixes, enhancing the interfacial adhesion EVA/calcium
kneader is described in Table 3. The compounds were pelletized and
carbonate (CaCO3) and EVA/ATH composites [6].
then dried for 3 hours at 80 °C prior to processing in the extruder.
After drying the materials were extruded on a Brabender single
2. Experimental screw (25 L/ D) extruder and conditions recorded (see Table 4
and Fig. 2).
2.1 Materials
Compounds developed in this paper were prepared with EVA i Table 3 Mixing procedure for compounds prepared in an internal
copolymer (VA content = 27 wt%; Melt Flow Index 3 g/10min; mixer.
Density = 0,951 g/cm³), EVM ii (VA Contents = 45±1,5 wt %,
MFI (190°C/2,16 Kg) = 2,5 g/10 min, ML1+4/100°C = 20±4 MU,
Temperature 60 [°C]
Density = 0,99 g/cm³ and 80±1,5 wt %, MFI (190°C/2,16 Kg) = 4
Rotor Speed 50 rpm
g/10 min, ML1+4/100°C = 28±6, Density = 1,11 g/cm³); Maleic Additon of Polymer 30 [s]
Acid modified LLDPE iii Melt Flow Index (190°C/2,16 Kg) = Additon of Filler+Additives 90 [s]
1,5g/10 min, Density = 0,93 g/cm³, Fine precipitated ATHiv BET Sweep 60 [s]
= 3,5 m²/g, D50 = 1,3 μm, Density = 2,4 g/cm³; Maleic Acid Mixing 60 [s]
modified EVMv (VA Content = 45±1,5 wt %, MFI (190°C/ 2,16 Total Time 240 [s]
Kg) = 0,8 g/10 min, Density = 1,05 g/cm³, Stabilizervi: Processing
Single Screw Extruder Processing parameters:
Screw compression: 2:1
i Die: 20*2*100 mm
Escorene® UL 00328 from Exxon Mobil Chemical
ii
Levapren® 450 HV, 800 HV from LANXESS Temperature setting: 130-140-145-150 °C
iii ®
Fusabond E MB-226DY from Dupont
vii
iv
Apyral® 40CD from Nabaltec Genioplast® S P
v ® viii
Levamelt MA 450 VP from LANXESS Mikrosöhl® Calcium Carbonate from VK Damman KG
vi ® ix
Irganox 1010 from Ciba Exact® 0210 from DSM/Exxon Mobil Chemical Joint Venture

International Wire & Cable Symposium 126 Proceedings of the 57th IWCS
 Table 4 Processing parameters for developed compounds. Melt Flow Index of Compounds
Screw Speed=85 rpm C1 C2 C3 C4 C5 C6 C7 C8 A clear reduction of MFI (see figure 7) for compounds containing
Torque 30,9 33,2 38,1 36,2 27,1 31,2 35,4 34,2 MA-g-LLDPE (C1 to C4) can be observed against compounds
Melttemp. T4 160 160 160 161 160 160 161 161 containing MA-g-EVM (C5 to C8).
Pressure D1 239 265 301 285 234 255 294 274
Pressure D2 87 97 107 104 88 91 106 100 This difference in MFI could be attributed to two factors:
Pressure D3 43 48 54 53 44 46 53 49
Output 59 61,8 67,8 66,6 49,4 61,6 63,9 66 a) Lower MFI of MA-g-EVM compared to the modified LLDPE
Meltviscosity 604 629 625 614 710 598 672 622
b) A higher interaction with the filler due to the higher VA content
of the MA-g-EVM
The compounds containing EVM (80% VA) have a lower MFI than
compounds containing EVM (45% VA) for both compatibilizers
used. This is mainly due to the higher Mooney viscosity of this
polymer and its effect in the overall viscosity of the compounds. It
can also be assumed that EVM 80 wt % VA contributes to
increasing filler-polymer interactions, mostly because of the high
VA content of one product against the other (EVM 80 wt % versus
45 wt % VA). Higher filler loading also leads to a lower MFI as can
be seen in the compounds with added calcium carbonate (CaCO3) in
compounds C3, C4, C7 and C8 (see figure 7 and 8).
Figure 2: Diagram of Brabender single screw extruder sensors for Despite the lower MFI values the melt viscosities remain on a fairly
monitoring of processing parameters similar level. Even more important, the throughput rates are not
much affected. Traditionally MA-g-LLDPE is used for enhancing
the compatibility between polar components and non polar ones to
increase compound throughput. A similar effect can be observed in
2.3 Testing Procedure compounds prepared with MA-g-EVM even despite the fact that the
MFI for these compounds is much lower than those of compounds
All material testing was performed according to the following prepared with MA-g-LLDPE (Fig. 7, 8 and 9). It also seems that the
ASTM procedures: EVM 80 wt % VA content is beneficial in case of compounds with
• ISO 5660: Cone Calorimeter, 50 kW/m2 high filler loading contributing to increasing throughput rate.

MA-g-LLDPE
• ASTM E 662: NBO Gas Chamber (Smoke density) 14,0

12,0
• ASTM D2863: Limiting Oxygen Index (LOI)
10,0
• ASTM D 412 Tensile Test
8,0

• ASTM D 2240 Hardness Shore A and D 6,0

4,0
• ASTM D 471 Hot Air Ageing
2,0
• ASTM D 573 Immersion in IRM Oil 902
0,0
CA C1 C2 CB C3 C4
• DIN EN ISO 1133 Melt Flow Index (MFI)
Figure 7: Melt Flow Index 21,6 Kg at 150°C for compounds
• ASTM D 1646 Mooney Viscosity prepared with MA-g-LLDPE

3. Results and Discussions

After systematic studies on miscibility and processability of EVA,

polymer compatibilizers, EOC and EVM as modifiers for
thermoplastic compounds, the present work is concentrated on
examining the effects of two different compatibilizers in compounds
using EVM 45 and 80 wt % VA as modifiers for enhancing the
elongation at break, oil resistance and flame retardant properties.
Furthermore, rheological, mechanical, flame tests and
morphological characterizations of these compounds were carried
out.

International Wire & Cable Symposium 127 Proceedings of the 57th IWCS
 of tensile properties as observed in figures 10 and 11. High values of
MA-g-EVM tensile strength and elongation at break were observed in compound
9,0
C2 and C4 prepared with EVM 80 wt% VA. In the case of C2 these
8,0 results can be explained by a better compatibility between ATH and
7,0 EVM 80 wt% through higher incorporation of the filler in the polar
6,0 matrix and therefore more effective filler-polymer interactions. The
high flexibility could be attributed to the modifying effect of EVM
5,0
copolymer on mechanical properties of polyolefins which was
4,0 studied recently. Serenko et al [7] have found that the modification of
3,0 polyolefins (LDPE) with EVA copolymer results in an enhancement
2,0 of the material toughness due to the increase of the adhesive
1,0
strength at the matrix-rubber particle interface. Ray and Khastgir [8]
have found that an interpenetrating polymer network-like structure
0,0
was formed in LDPE/EVA blends with a minimum of 50 wt% EVA
CC C5 C6 CD C7 C8
in the blend. The tensile strength and the elongation at break of
different LDPE/EVA blends improved with increase of EVA
Figure 8: Melt Flow Index 21,6 Kg at 150°C for compounds content up to 50 wt % after which the change is marginal. With
prepared with MA-g-EVM increasing VA content, EVM copolymers become softer due to the
decrease of crystallinity. Compounds with up to 40 wt % VA are
soft elastic and highly fillable. Furthermore, they are more resistant
to dilute mineral acids, alkaline substances, alcohols, fats, oil and
80 Torque [N/m]
Output [g/m in]
detergents. The resistance to environmental stress cracking (ESC)
67,8 66,6
70 65
61,8
65,4 increases as well with an increase of VA content and decreasing of
59
60 MFI [9].
50
40,3 38,1
40 33,2
30,9
30

20
MA-g-LLDPE
10 11,0 10,5
10,3
0
10,0 9,6
Tensile Strength [MPa]
3

3
t%

t%
CA

9,1
B

9,0
C

aC

aC
w

9,0
5

+C

+C
=4

=8

0%
VA

VA

7,9
45

8,0
=8
=
VA

VA

7,0

Figure 8: Torque and output for compounds prepared with MA-g- 6,0
LLDPE
5,0
t%

t%

3
A

O
C

C
w

aC

aC
5

+C

+C
=4

=8

5%

0%
VA

VA

80 Torque [N/m ]
=4

=8
70,4
VA

VA
Output [g/m in]
70 63,9 66
61,6
60
58
Figure 10: Tensile strength for compounds containing MA-g-
49,4
50 LLDPE (C1-C4 and references CA and CB)
39,8
40
31,2
30 27,1
23,6
MA-g-LLDPE
20 350
10 300
Elongation at Break [%]

263
0 250
207 205
192
t%

t%

3
C

200
O

176
C

C
w

aC

aC
5

+C

+C
=4

=8

150 133
5%

0%
VA

VA

=4

=8

100
VA

VA

50
Figure 9: Torque and Output for compounds prepared with MA-g- 0
EVM
A

t%

t%

3
O

O
C

C
w

aC

aC
5

+C

+C
=4

=8
VA

VA

5%

0%
=4

=8

Mechanical Properties
VA

VA

The three main mechanical properties measured in this study were: Figure 11: Elongation at break for compounds containing MA-g-
Tensile strength, Elongation at break and hardness Shore A and D. LLDPE (C1-C4 and references CA and CB)
Compounds prepared with MA-g-LLDPE displayed a good balance

International Wire & Cable Symposium 128 Proceedings of the 57th IWCS
Tensile strength values of all compounds prepared with EVM 80 wt MA-g-LLDPE
% VA are slightly higher than those of compounds prepared with 110
96 94 94
EVM 45 wt % VA, independently of the compatibilizer used. All in 100 94
89
94
90
all tensile strength of compounds prepared with MA-g-LLDPE was 80

Hardness
higher than TS of those prepared with MA-g-EVM, this 70 Shore A
Shore D
compatibilizer is a rubbery polymer and thus cannot have the same 60
50 42
reinforcing effect as a crystalline LLDPE polymer based 40 35 36
40

compatibilizer. Nevertheless this material contributes to improve 30 26 26

elongation at break and to a decrease of hardness Shore A and D 20

10
when compared with compounds prepared with MA-g-LLDPE
(figures 14 and 15). The plasticizing effect of both rubbers used

t%

t%

3
O

O
C

C
w

aC

aC
5

0
could be clearly seen on figures 11 and 13 whereas rubber modified

+C

+C
=4

=8
VA

VA

5%

0%
compounds displayed better values of elongation at break than the

=4

=8
VA

VA
corresponding references (CA-CD).
Figure 14: Hardness Shore A and D for compounds containing
MA-g-LLDPE (C1-C4 and references CA and CB)

MA-g-EVM
9,0 8,7

8,5
Tensile Strength [MPa]

MA-g-EVM
8,0
110
100 95
90 92 91 91 92
7,5 7,2
90
7,0 6,7 80
6,6

Hardness
6,5 6,3 70
6,2
Shore A
6,0 60 Shore D
50
5,5
40 35 32 33 35
5,0 28 30
30
20
t%

t%
C

3
O

O
C

C
w

aC

aC

10
5

+C

+C
=4

=8
VA

VA

5%

0%

t%

t%
C

3
O

O
C

C
=4

=8

aC

aC
VA

VA

+C

+C
=4

=8
VA

VA

5%

0%
=4

=8
Figure 12: Tensile strength for compounds containing MA-g-EVM

VA

VA
(C5-C8 and references CC and CD) Figure 15: Hardness Shore A and D for compounds containing
MA-g-EVM (C5-C8 and references CC and CD).

MA-g-EVM
350 321
303
Atom Force Microscopy
300
Elongation at Break [%]

250 225
The compatibilizing effect of EVM grades can be seen in the AFM
200
189 micrographs obtained for Compounds C1 and C2. The high polarity
150
of EVM 80 wt % VA contributes to the increase in the adhesion to
100
96 polar fillers (ATH). This effect is demonstrated in figure 16 and 17
72

50
where the dark brown rubbery phase is surrounding the filler
0
particle (light yellow) showing the improved the interfacial adhesion
between ATH and EVA matrix [2]. Despite the fact that MA-g-
t%

t%

3
C

LLDPE and MA-g-EVM are used with the purpose of improving

C

C
w

aC

aC
5

+C

+C
=4

=8

5%

0%
VA

VA

this interfacial adhesion between the ATH and the EVA matrix, the
=4

=8
VA

VA

EVM 45 and 80 wt % VA materials have an even stronger tendency

Figure 13: Elongation at break for compounds containing MA-g- to coat the fillers mainly due to their high polarity and its ability to
EVM (C5-C8 and references CC and CD) promote a better interaction (van der Waals forces) with the
functional OH groups on the surface of the ATH. This ability
directly correlates with the increase of the VA content, therefore a
more pronounced coating effect is observed in compound C2 when
compared with C1 which was prepared with EVM 45 wt % VA.

International Wire & Cable Symposium 129 Proceedings of the 57th IWCS
 MA-g-LLDPE
Weight [%]
50
Volum e [%]
40 TS [%]
31 EB [%]
30 25,57 26,58
23
19
20 15,83 15,23 16,70
12,84 13,77 13,62
9,55 7,96 8,48 9 8,21
10

Variation [%]
1
0

3
t%

t%
A

B
-5

O
-10

aC

aC
w

w
5

+C

+C
=4

=8

5%

0%
VA

VA
-20 -16

=4

=8
-19

VA

VA
-23 -23
-30 -26 -25

1 μm -40

-50

Figure 16: AFM micrograph of compound C1 showing Figure 18: Variation of properties after immersion in Oil N° 902 for
macromolecular morphology (Cross section - 2,5 μm x 2,5 μm) 4h at 70°C in compounds prepared with MA-g-LLDPE (C1-C4 and
references CA and CB)
MA-g-EVM 28
30
22,48 21,37 21,11
20,82 20,42
19 19,18
20 15
13,15 13,69 12,54 13,75 12,50
11,03
10

0
0

Variation [%]
-2

3
D
-3

t%

t%

O
C
C

aC

aC
w

w
-10

+C

+C
=4

=8

5%

0%
VA

VA

=4

=8
VA

VA
-20 -16

-24
-30
-31
-33
-40 Weight [%]
-42 -41 Volum e [%]
TS [%]
-50
EB [%]

Figure 19: Variation of properties after immersion in Oil N° 902

for 4h at 70°C in compounds prepared with MA-g-EVM (C5-C8
1 μm and references CC and CD)

Hot Air ageing 10 days at 100°C

Figure 17: AFM micrograph of compound C2 showing
macromolecular morphology (Cross section - 2,5 μm x 2,5 μm)
Immersion in IRM 902 Oil
All compounds were immersed in IRM N° 902 oil for 4 hours at
70°C, and the variation of weight, volume, tensile strength and
elongation at break was measured as observed in figures 18 and 19.
Variation of properties for compounds prepared with MA-g-LLDPE
was in general lower than the variation of properties for compounds
prepared with MA-g-EVM. Change in weight and volume in
The hot air ageing resistance for compounds prepared with MA-g-
LLDPE was better than those prepared with MA-g-EVM. This
could be attributed to two main reasons: a) the typical heat
stabilization additives such as MgO had not yet been used and
therefore any possible effect of accelerated polymer degradation by
acid groups cannot be properly controlled and b) a moderate heat
treatment may lead to more intense interaction of ATH fillers and
polar polymers reducing the elongation at break of compounds.
Retention of properties after hot air in reference compound CA is
equivalent to compounds prepared with EVM 45 and 80 wt% VA.
MA-g-LLDPE
20
Delta TS

compounds with EVM 80 wt % VA was much lower when Delta EB

Delta H
compared with compounds prepared with EVM 45 wt % VA for 10 6
both compatibilizers used in this study. The high level of polarity 0 1 2
0
2
0 2
0
0
provided by 80% VA groups contributes to improve the resistance
Variation [%]

-1 -2 -1 -1
-3
t%

t%

to oil of these compounds. However variation of tensile strength and

A

O
C

C
w

aC

aC

-10
5

+C

+C

elongation at break is more accentuated for compounds

=4

=8

5%

0%
VA

VA

-12
=4

=8

-15
compatibilized with MA-g-EVM. A possible cause for these results -20 -17
VA

VA

-18
can be the temperature used for the immersion test. At 70°C the
-30
EVA base polymer is not completely decrystallized and the residual
crystallinity contributes to oil resistance. The effect of CaCO3 in -40
compounds prepared with both compatibilizers can be clearly
observed especially in the variation of elongation at break for Figure 20: Variation of Properties after Hot air ageing for 10 days
compounds with EVM 45 wt % VA; this effect can be attributed to at 100°C in compounds prepared with MA-g-LLDPE (C1-C4 and
the higher filler loading with less swellable polymer. references CA-CB)

International Wire & Cable Symposium 130 Proceedings of the 57th IWCS
 MA-g-EVM MA-g-LLDPE Tensile Strength, at -15 °C
Delta TS 25
20 Delta EB
Delta H

10
5 5 4 5 20
3 3
0 0 0 1
0
Variation [%]

-2
-4 15
t%

t%
C

Stress [MPa]
O

O
C

C
w

aC

aC
-10
5

+C

+C
=4

=8
-10
VA

VA

5%

0%
=4

=8
-20

VA

VA
-18 10
-22

-30 -29
EVM 45 wt % VA
-30 EVM 80 wt % VA
5
EVM 45 wt % VA+CaCO3
-36
-40 EVM 80 wt % VA+CaCO3
CC
CD
0
Figure 21: Variation of properties after Hot air ageing during 10 0 10 20 30 40 50 60 70 80
days at 100°C in compounds prepared with MA-g-EVM (C5-C8 Elongation [% ]

and references CC and CD)

Figure 23: Tensile strength at -15°C after 4 hours conditioning in
compounds prepared with MA-g-EVM (C5-C8 and references CC
Mechanical Properties at Low Temperature (-15°C) and CD)
The tensile properties of compounds were tested at -15 °C, and Limiting Oxygen Index (ASTM D 2863)
the stress-strain curves for compounds prepared with MA-g-
Generally speaking, LOI results obtained for compounds containing
LLDPE are shown in figure 22. Compounds prepared with EVM
EVM 80 wt % VA are much higher than those of compounds
45 wt % VA as modifier reported the best elongation at break of
containing EVM 45 wt % VA, independently of the type of
all compounds prepared with MA-g-LLDPE with and without
compatibilizer used (figures 24 and 25). This effect was described
CaCO3. This effect can be explained due to the low Tg of this
by Rohde who found a better LOI performance with increasing of
polymer and the plasticizing effect of this rubbery product in the
vinyl acetate content starting at approximately 50 wt % VA where
EVA 27 wt % VA resin based compound. Elongation at break is
the increase of the LOI is disproportionally greater than expected
affected by higher filler loading as can be seen in figures 22 and
from linear extrapolation of combustion enthalpy in highly ATH
23 for those compounds prepared with CaCO3. When comparing
filled compounds [3].
compounds prepared with MA-g-EVM with those prepared with
MA-g-LLDPE a much lower elongation at break can be MA-g-LLDPE
50
appreciated possible due to poor Compatibilizing effect of MA-g-
Limiting Oxygen Index [%]

EVM in this specific formulation. 45

40 40
40 39
37
35
35 33
MA-g-LLDPE Tensile Strength, at -15 °C
25
30

25
20
20
A

t%

t%

3
O

O
C

C
w

aC

aC
15
Stress [MPa]

+C

+C
=4

=8
VA

VA

5%

0%
=4

=8
VA

VA

10
EVM 45 wt % VA Figure 24: Limiting oxygen index in compounds prepared with
EVM 80 wt % VA
EVM 45 wt % VA+CaCO3 MA-g-LLDPE (C1-C4 and references CA and CB)
5 EVM 80 wt % VA+CaCO3
CA MA-g-EVM
CB 50
Limiting Oxygen Index [%]

0 45
0 20 40 60 80 100 120 140 160 180
39
40 38
Elongation [% ] 37
36
35
34
35
Figure 22: Tensile strength at -15°C after 4 hours conditioning in
30
compounds prepared with MA-g-LLDPE (C1-C4 and references
CA and CB) 25

20
t%

t%
C

3
O

O
C

C
w

aC

aC
5

+C

+C
=4

=8
VA

VA

5%

0%
=4

=8
VA

VA

Figure 25: Limiting oxygen index in compounds prepared with

MA-g-EVM (C5-C8 and references CC and CD)

International Wire & Cable Symposium 131 Proceedings of the 57th IWCS
Cone Calorimetry (ISO 5660) 5. Acknowledgments
Table 5 summarizes the cone calorimeter results. The cone Special thanks to Mr. Östreich and Mr. Taschner for the valuable
calorimetry parameters includes time to ignition (TTI), peak heat support on the preparation and testing of all samples generated for
release (PHRR), total heat release (THR), mass loss rate (MLR), this paper.
heat release rate at 180 s HRR (180), heat release rate at 300 s HRR
(300), enthalpy heat of combustion (EHC), total smoke release 6. References
(TSR), carbon monoxide yield (CO) and carbon dioxide yield
[1] Nexans “Shipbuilding White Paper: Bringing safety onboard
(CO2).
through better cabling solutions” September (2007).
[2] Ling Zhang, Chun Zhong Li, and Qiuling Zhou “Aluminium
Table 5 Results of Cone Calorimetry according ISO 5660 hydroxide filled ethylene vinyl acetate (EVA) composites:
effect of the interfacial compatibilizer and the particle size”
t(ig) HRR (peak) THR HRR(180) HRR(300) MLR EHC TSR CO CO2 Journal of Material Science, (2006).
[s] [kW/m²] [MJ/m²] [kW/m²] [kW/m²] [g/s*m²] [MJ/kg] [m²/s] [kg/kg] [kg/kg]
CA 43,7 191,73 25,61 110,25 76,87 4,1 21,77 269,46 0,04 2,47 [3] E. Rohde “Ethylene Vinyl Acetate Elastomers: Applications
C1 52,0 214,16 29,07 128,35 90,44 6,4 26,07 356,55 0,04 2,60
C2 46,3 215,38 23,42 107,97 73,64 4,6 21,62 349,54 0,04 2,26 and Opportunities for Industrial Rubber Goods” 141st
CC 42,0 183,46 23,39 101,59 69,32 3,6 22 317,64 0,05 2,51 Meeting of the Rubber Division American Chemical Society,
C5 50,0 269,71 23,23 108,24 72,39 5,4 21,65 225,73 0,05 2,34
C6 48,7 194,94 22,80 102,41 67,31 5,5 21,97 266,05 0,06 2,37 Proceedings (1992).
CB 47,3 231,22 23,63 102,86 69,05 2,9 19,50 227,13 0,05 2,33
C3 45,3 196,31 22,12 105,07 67,90 4,4 21,79 264,24 0,06 2,46 [4] K. Naskar, S. Mohanty and G.B. Nando “Development of
C4 48,7 194,94 22,80 102,41 67,31 5,5 21,97 349,04 0,05 2,34 Thin-Walled Halogen Free Cable Insulation and Halogen-
CD 47,0 251,68 18,49 90,62 58,36 3,51 17,89 193,29 0,06 2,11
C7 46,3 235,41 26,26 108,12 74,42 4,8 24,53 348,49 0,05 2,32 Free Fire-Resistance Low Smoke Cable” Journal of Applied
C8 51,3 218,35 21,32 98,07 64,87 5,5 21,58 296,5 0,07 2,45 Polymer Science, Vol. 104, 2389-2848 (2007)
[5] Tong Chen, Alex Isarov “New magnesium Hydroxides
Compounds C2, C6, C4 and C8 with EVM 80 wt % VA displayed Enabling Low-smoke Cable Compounds” Proceedings of the
the lower values of HRR peak, HRR (180), HRR (300) as well as 56th IWCS (2006)
EHC when compared to compound prepared with EVM 45 wt % [6] Zhengzhou Wang, Baojun Qu, Weicheng Fan, Yuan Hu,
VA. The THR values for compounds modified with EVM 45 and Xiaofeng Shen “Effects of PE-g-DBM as a compatibilizer on
80% are lower than those of the reference compounds. This might mechanical properties and crystallization behaviours of
be related to the lower enthalpy of combustion of polymers with magnesium hydroxide-based LLDPE blends” Polymer
high VA content. The compounds prepared with MA-g-LLDPE degradation and Stability 76, 123-128 (2002).
displayed a better range of flame retardant properties than those [7] O. A. Serenko, V. S. Avinkin “Influence of an Ethylene
prepared with MA-g-EVM. Low values of HRR (peak), HRR (300), Vinyl Acetate Copolymer on the mechanical properties of a
EHC and TSR were measured in reference compounds CC and CD LLDPE filled blend” Polymer Science 43, 129-133 (2001).
prepared with MA-g-EVM when compared with compounds
prepared with MA-g-LLDPE what might be a result of the good [8] I. Ray, D. Khastgir “Correlation between morphology with
compatibilizer effect of the MA-g-EVM material. dynamic mechanical, thermal, physico-mechanical properties
and electrical conductivity for EVA-LDPE blends” Polymer,
34, 2030-2037 (1993).
[9] Bistra Andersen “Investigation on Environmental Stress
4. Conclusions cracking resistance of LDPE/EVA blends” Dissertation
In this study we investigated the effect of introducing two different
Martin Luther Universität Halle-Wittenberg (2004).
kinds of rubbery modifiers, EVM-45%VA and EVM-80% VA into
typical EVA based HFFR or low smoke zero halogen (LSZH) [10] A. A. Basfar, J. Mosnáček, T. M. Shukri, M. A. Bahattab, P.
thermoplastic cable compounds. The effect of a maleic acid Noireaux, A. Courdreuse “Mechanical and Thermal
anhydride grafted EVM compared to MA-g-LLDPE was also properties of LDPE and EVA crosslinked by both Dicumyl
studied. Peroxide and Ionizing radiation for Wire and Cable
Applications” Journal of Applied Polymer Science, Vol. 107,
EVM-80% VA improves both tensile strength and elongation at
642-649 (2008).
break; it also provides higher throughput in highly filled compounds.
The use of MA-g-EVM-45% VA instead of the thermoplastic [11] A. Nakayama, H. Kimura, K. Watanabe, Y. Kondo, Y. Ota
LLDPE-based compatibilizer creates softer compounds with lower and S. Iwata “Development of Ecological Wire and Cable
tensile strength and higher elongation. It appears that the total (ECO-GREEN)” Hitachi Cable Review N°18 (1999)
amount of rubbery polymer in thermoplastic compounds must be [12] D. Duphil, B. Poisson, P. Argaut, J. Barbeta, C. Pascual, J.
limited to preserve the strength provided by the thermoplastic back- Martinez “Choices of Flame Retardant materials for Cables
bone polymers. In terms of oil or grease resistance EVM-80% VA with Improved Behaviour in Fire” Jicable Proceedings
offers advantages over lower VA polymers in non-cured compounds (2007)
with thermoplastic polymers. [13] Zhengzhou Wang, Baojun Qu, Weicheng Fan, Yuan Hu,
A general improvement of flame retardant properties is observed in Xiaofeng Shen “Effects of PE-g-DBM as a compatibilizer on
compounds containing MA-g-EVM and EVM 80 wt % VA when mechanical properties and crystallization behavior of
compared to compounds containing MA-g-LLDPE and EVM 45 wt magnesium hydroxide-based LLDPE blends” Polymer
% VA; this improvement is mainly observed in lower smoke Degradation and Stability 76, 123-128 (2002).
production rate and lower smoke density of prepared compounds.

International Wire & Cable Symposium 132 Proceedings of the 57th IWCS
 [14] Tong Chen, Allen Hendrix “The Characteristics of Non-
Halogen Flame Retardant Compound using Advanced
Thermoplastic Plastomer” Proceedings of the 51st IWCS
(2002).
[15] Peter R. Hornsby “Maximizing the Fire Retarding
Performance of Hydrated Mineral Fillers” 18th Annual BCC
Conference in Flame Retardancy, (2007).
[16] Mingqian Zhang, Uttandaraman Sundararaj “Thermal
Rheological and Mechanical Behaviors of
LLDPE/PEMA/Clay Nanocomposites: Effect of Interaction
between Polymer, Compatibilizer and Nanofiller”
Macromolecular Materials and Engineering 291, 696-706,
(2006).
[17] Jordi Grabolosa, Daniel Calveras, Isabelle Canerot “Use of
Nanofillers in High Performance of MV Cables under Fire
Conditions” Jicable proceedings (2007).
Martin Hoch, 49 years old, based in Shanghai as a regional
[18] Dipak Rana, Hak Lim Kim, Hanjin Kwag, Soonja Choe
product and technical manager focusing on EVM at LANXESS
“Hybrid Blends of similar ethylene 1-octene copolymers”
Chemical (Shanghai) Co, Ltd. He had worked with former Bayer
Polymer 41, 7067-7082, (2000).
in R&D positions for latex, adhesives and specialty elastomers,
[19] K. Hausmann “High Performance Coupling Agents for involved in production process improvement, products
HFFR and W&C Compounds” Proceedings Cables 2007. development and more recently in technical marketing. He
[20] Soochul Park and Soonja Choe “The Compatibilizing Effect obtained his doctorate at the Hamburg University in Germany
of Maleic Anhydride in Ethylene-Vinyl Acetate with a thesis related to metal-organic chemistry.
(EVA)/Ethylene-α-Olefin Copolymers Blends”
Macromolecular Research Vol. 13 N°4, 297-305, (2005).

THE AUTHORS

Albertus Tankink, 57 years, works as Sales and Technical

Marketing manager for the modification of plastics with
elastomers at LANXESS Deutschland GmbH. He worked 13
years with Polysar as Development specialist for plastic modifiers
Manuel La Rosa, 33 years old, works as Sales and Technical and 12 years with CIAGO in R&D and customer services for
Marketing manager for the Wire & Cable Industry in Europe synthetic latex and thermoplastic Polyurethanes.
since 2005 at LANXESS Deutschland GmbH. Mainly focused in
high performance rubbers for cables used in high end markets (Oil
& Gas, Wind, Solar, railways, navy and Defense). In 2006 he
accomplished the “Rubber Technology Course” at the Leibniz
Universität Hannover and German Rubber Institute. He worked
four years at Rhodia Engineering Plastics as Application and
Product development Engineer for Polyamides covering
Scandinavia, UK and Germany. His thesis degree work was
conducted at BMW AG in the area of Aliphatic Polyurethanes in
car interiors. In September 2000 he graduated in Caracas
Venezuela at the Universidad Simón Bolívar obtaining a degree in
Material Science Engineering (Polymers).

International Wire & Cable Symposium 133 Proceedings of the 57th IWCS

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