Thermogravimetry and swelling characteristics af NBR/EPDM blends with some

compatibilizers
Hesty Eka Mayasari, and Noor Maryam Setyadewi

Citation: AIP Conference Proceedings 2049, 020042 (2018); doi: 10.1063/1.5082447

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Published by the American Institute of Physics
 Thermogravimetry and Swelling Characteristics af
NBR/EPDM Blends with Some Compatibilizers

Hesty Eka Mayasari 1, a) and Noor Maryam Setyadewi 1,b)

1
Center for Leather, Rubber and Plastics, Ministry of Industry, Jl. Sokonandi No. 9 Yogyakarta, 55166, Indonesia.
a)
Corresponding author: [email protected]
b)
[email protected]

Abstract

The blending of two or more rubber can provide a non-homogeneous blend. Compatibilizer can be used to make a more
homogeneous rubber blend. Methyl methacrylate-butadiene-styrene (MBS), bromobutyl rubber (BIIR), and zeolite are
used as the compatibilizer in nitrile butadiene rubber/ ethylene propylene diene monomer (NBR/EPDM) blend in this
study. This study aims to determine the thermogravimetry and the swelling characteristics of NBR/EPDM blend.
NBR/EPDM blend was prepared by a two-roll mill. The vulcanizate was tested with a thermogravimetric analyzer with a
heating rate of 10, 15, and 20°C at 30-600°C and immersed in IRM oil, toluene, and n-hexane to determine the swelling
characteristics. The degradation of NBR/EPDM blend consists of two stages. The kinetic parameters of the degradation
process were studied by applying the Coats and Redfern method. The BIIR as compatibilizer results in the highest
activation energy at each stage (24.71 and 20.78 kJ/mol). The MBS result the largest final mass at 600°C (39.63-42.62 %)
and also provide the best swelling resistance in IRM, toluene, and hexane. MBS is a suitable compatibilizer for
NBR/EPDM blend to get a good thermal and swelling resistance.

INTRODUCTION
Many studies recently focused on mixing two or more polymers to get the better product, improve the
process and the cost. Each polymer has their own properties that can be mutually reinforcing if used simultaneously
rather than being used singly. Nitrile rubber (NBR) has good mechanical properties and resistance to fuel and oil.
NBR has poor resistant to ozone and weather. The ethylene-propylene-diene monomer (EPDM) has good
compression properties, resistance to ozone, oils, chemicals, and heat [1, 2]. The nonpolar EPDM make it has
excellent resistance to polar solvents and chemicals [3]. However, EPDM has poor mechanical properties and
sensitive to oxidation [1].
The blending between two rubber is expected to produce better products with excellent resistance to oil,
fuel and have good resistance to heat and ozone. But, NBR and EPDM have different polarity and saturation
properties that can provide an incompatible blend. In polymer blending, it is necessary to consider both blending
techniques and additives. The polymer blending can result in a non-homogeneous blend that can produce the final
product with poor properties. To prevent this phenomenon, some previous researchers used compatibilizer [4, 5].
Compatibilizer gives the better dispersion, improve the interfacial adhesion, and reduce the interface energy between
phases that could make the blend become more homogeneous [6, 7]. The compatibilizers used in this study are
methyl methacrylate-butadiene-styrene (MBS), bromobutyl rubber (BIIR), and zeolite.
The rubber product will be degraded after being exposed by heat at a certain time. The decreasing physical
properties of the rubber product happens because of this phenomenon. The thermogravimetry test is the common
method to study the thermal characteristics of the material. From this test, it will give information about the initial
degadration time and temperature, the mass loss, and the degradation stage. Knowledge about the thermogravimetry
characteristics is very important to get information about the application and storage conditions [8]. The interaction
between the polymer and the solvent is also important to be studied. The properties of rubber products that contact

The 3rd International Seminar on Chemistry

AIP Conf. Proc. 2049, 020042-1–020042-7; https://doi.org/10.1063/1.5082447
Published by AIP Publishing. 978-0-7354-1775-5/$30.00

020042-1
with oil or fuel will decrease. The swelling characteristic of the polymer is important to be studied to know the
polymer resistance in the solvent.
There have been many studied about the blending of NBR/EPDM [9, 10, 11]. However, there are still
limited studies that examine the thermogravimetric and swelling characteristics of NBR/EPDM blend especially by
using compatibilizer. It is important to know the most suitable compatibilizer for the NBR/EPDM [8, 12]. This
research study about the thermogravimetry and swelling characteristics of NBR/EPDM blend with MBS, BIIR, and
zeolite compatibilizer. This is the second publication from the previous study by Mayasari et al. [13]. Previous
publication evaluated the kinetic vulcanization and the mechanical properties of NBR/EPDM blend. In this study,
the thermogravimetry and swelling characteristics of NBR/EPDM blend will be studied by using thermogravimetry
analysis (TGA) method and by immersed the NBR/EPDM blend in IRM, toluene, and n-hexane. The purpose of this
publication was to study the thermogravimetry and swelling characteristics of NBR/EPDM blend with some
compatibilizer. So that, it can be known the appropriate compatibilizer and the most suitable storage and application
conditions of NBR/EPDM blend.

MATERIALS AND METHOD

NBR (Krynac 4975 F) and EPDM (Keltan 4551 A) were used in this study as the previous study [13]. The
fillers are carbon black N330 High Abrassion Furnace (HAF) and N774 Semi Reinforcing Furnace (SRF) (OCI,
Korea). The additives are paraffin wax Antilux 654 A, paraffinic oil from Indrasari, zinc oxide (ZnO ) Indoxide,
stearic acid Aflux 42 M ex Rhein Chemie, 6PPD ex Starchem, 2,2'- dithiobis (benzothiazole) (MBTS) Kemai, N-
cyclohexyl-benzothiazyl-sulphenamide (CBS) Kemai, methyl methacrylate-butadiene-styrene (MBS) ZB-521 ZB-
32 (Huaxing), BIIR Lanxess, natural Zeolite from the local market, and sulfur ex. Miwon.
NBR, EPDM, and additives were weighted according to the formulation and then it was milled with the
two-roll mill at 40 - 50 ºC. The compounds were conditioned for 24 hours at room temperature. A rheometer test
was carried out at 160 ºC. Then, the compounds were pressed according to the time of the rheometer with a
hydraulic press at a pressure of 150 kg/cm2. The research formulation is shown in Table 1. [13].

TABLE 1. Formulation of NBR/EPDM Compound

phr (part per hundred resin)
Materials
NEM NEB NEZ
NBR 50 50 50
EPDM 50 50 50
MBS 2.5 0 0
BIIR 0 2.5 0
Zeolite 0 0 2.5
Zinc Oxide 5 5 5
Stearic Acid 1 1 1
HAF CB N330 30 30 30
SRF CB N774 30 30 30
Paraffinic Oil 10 10 10
Paraffinic Wax 0.5 0.5 0.5
6 PPD 5 5 5
MBTS 1.5 1.5 1.5
CBS 0.5 0.5 0.5
Sulfur 1.5 1.5 1.5

Thermogravimetry and Swelling Characteristics

Shimadzu DTG 60 was used to observed the thermogravimetry characteristic. The nitrogen gas flowed at a
rate of 15 ml/min at 30-600 °C with a heating rate of 10, 15, and 20 °C/minute using an alumina container with 5-8
mg of NBR/EPDM powder sample.

020042-2
 The kinetic parameters were studied used the Coats Redfern equation as some previous study [14, 15] that
shown in Equation (1). Thermogravimetry (TG) is determined by measurement of degradation rate and fractional
mass loss according to temperature change.

(1)

-
In Equation (1), - linear with . The slope as is used to calculate the activation energy. The intercept is
used to calculate the pre-exponential factor. The first order reaction is assumed in this study.
Swelling test was performed at 23±2 °C for 72 h according to ISO 1817 by immersed the NBR/EPDM
blend in IRM 903, toluene, n-hexane. The change in mass was calculated by Equation (2).

-
(2)

Where is the mass of the test piece after immersion, is the mass of test piece before immersion.

RESULT AND DISCUSSION

Thermogravimetry and swelling characteristics are important to be studied. It can give valuable information
about performance of the blend. This information can be used to decided the most suitable storage and application
conditions of NBR/EPDM blend.

Thermogravimetry Characteristics
Thermal analysis can be used for product lifetime predictions to improve the product performance. The
thermogravimetry analysis measures the rate of degradation and fractional mass loss according to temperature
change. The TG analysis is used to determine the oxidative and thermal stabilities of materials [8]. The
thermogravimetric (TGA) curve and the derivatives thermogravimetric (DTG) curve of the NBR / EPDM blend are
shown in Fig. 1.
Figure 1 shows that all of the blend have similar thermogravimetric characteristics. Two stage of
degradation of the NBR/EPDM blends were observed. Two sharps peak indicates temperature in which the highest
degradation occurs. The first degradation stage is seen at 30ºC and was completed at around 207ºC. At this stage, the
evaporation moisture content occurs. The MBS, BIIR, and zeolite do not provide significant temperature differences
at the first degradation stage. The second stage occurs at 181-517 ºC. The former step at the second stage is the
releasing of the nonrubber materials and then the later step is the degradation of rubber. Here, a chain scission of
NBR/EPDM molecule occurs. The free radicals from the oxidation reaction after heating will attack the molecule
chain of NBR/EPDM blend. At the end of degradation process, the mass residue is about 36.64 42.62 %. EPDM is
perfectly degraded at 480-500 ºC [14, 16] and NBR is perfectly degraded at 590-610 ºC [17]. In this study, the
NBR/EPDM blend was perfectly degraded at 488-517ºC, between the perfect degradation temperature of EPDM and
NBR separately. The degradation stages of NBR/EPDM blends are shown in Table 2.
Table 2 shows that the variation of compatibilizer gives no significant mass residue differences. This may
happen because the mass residue mostly depends on the amount of filler in the blend. Table 2 shows that the higher
heating rate, the higher peak temperatures and initial temperatures of the second stage. But the heating rate gives no
effect on mass residue [18, 19]. From Table 2, it is known that the final mass of stage II for zeolite-blend is 38.26-
40.40 %, BIIR-blend is 36.64-38.28 %, and MBS-blend is 39.63-42.62%. MBS provides the highest end mass at 600
°C and BIIR gives the lowest end mass. This shows that MBS give the best heat resistance for NBR/EPDM blend.
This may happen because MBS as compatibilizer improves the interfacial adhesion between the filler-rubber [20].

020042-3
 1 0 0 0
8 0 0 5 0 0 1 0 0 0
6 0 N E Z - 0 .0 0 5 N E Z
4 0 N E B N E B
2 0 - 0 .0 1
N E M N E M
0
0 2 0 0 4 0 0 6 0 0 - 0 .0 1 5

(a) (b)
1 0 0 0
8 0 0 5 0 0 1 0 0 0
N E Z - 0 .0 0 5 N E Z
6 0
4 0 N E B - 0 .0 1 N E B
2 0 N E M - 0 .0 1 5 N E M
0
0 2 0 0 4 0 0 6 0 0 - 0 .0 2

(c) (d)
1 0 0 0
8 0 0 5 0 0 1 0 0 0
N E Z - 0 .0 0 5 N E Z
6 0
4 0 N E B - 0 .0 1 N E B
2 0 - 0 .0 1 5
N E M N E M
0
0 2 0 0 4 0 0 6 0 0 - 0 .0 2

(e) (f)
FIGURE 1. The thermogravimetric curve at a heating rate (a) 10°C (c) 15°C (e) 20°C and derivative thermogravimetric curve at
a heating rate (b) 10°C (d) 15°C (f) 20°C of NEZ, NEB, and NEM blend

TABLE 2. Degradation of NBR/EPDM blend

Heating Stage I Stage II
Code rate, °C Mass Residue, %
/min Temp., °C Peak temp., °C Temp., °C Peak temp., °C
10 30 - 180 92 181 - 500 466 38.26
NEZ 15 30 - 204 111 205 - 503 476 40.40
20 30 - 219 111 220 - 509 482 40.16
10 30 - 183 101 184 - 488 464 38.28
NEB 15 30 - 199 110 200 - 516 476 36.64
20 30 - 199 111 200 - 517 481 36.85
10 30 - 192 99 193 - 498 456 39.63
NEM 15 30 - 207 109 208 - 512 472 40.45
20 30 - 199 111 200 - 515 480 42.62

Kinetic parameters
The activation energy and pre-exponential factor can be calculated by the thermogravimetry data. Plotting
-
- versus from Eq. (1) give the result as shown in Table 3.

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 Table 3 shows the activation energy and pre-exponential factors of NBR/EPDM blend. Activation energy is
the energy needed to initiate degradation and break the chemical chain bonds. The NBR/EPDM blend require
activation energy of 15.59 to 24.72 kJ/mol for stages I and 20.05 to 20.78 kJ/mol for stage II. MBS provides the
lowest activation energy at stage I and stage II, whereas BIIR provides the highest activation energy. High activation
energy indicates the high crosslinking density on the blend, resulting in high energy required to break the bond [8].
This is in accordance with the previous study showing that BIIR provides the highest crosslinking density [13].

TABLE 3. Energy activation and pre-exponential factor of NBR/EPDM blend

Heating Ea, kJ/mol A, min-1
Code rate,
°C/min Stage I Average Stage II Average Stage I Average Stage II Average
10 26.11 19.46 0.00145 0.00009
NEZ 15 21.80 23.33 20.65 20.56 0.00036 0.00072 0.00010 0.00010
20 22.08 21.56 0.00035 0.00012
10 23.87 16.96 0.00095 0.00006
NEB 15 23.87 24.72 23.95 20.78 0.00095 0.00103 0.00020 0.00012
20 26.41 21.44 0.00120 0.00011
10 16.86 20.15 0.00005 0.00010
NEM 15 20.98 15.59 23.61 20.05 0.00024 0.00010 0.00018 0.00011
20 8.93 16.40 0.00001 0.00004

Swelling Characteristics
The polymer materials that contact with different solvents during application is known as swelling. The
swelling density of polymer expressed as the amount of liquid absorbed by the polymer. The effect of different
solvent in NBR/EPDM blends is shown in Fig. 2.
The phenomenon of swelling occurs in two conditions, the reduction of mass and the addition of mass. This
mass reduction makes the final product shrink. This shrinking condition is not preferred if it is applied as seal or
gasket, as it may cause leakage. IRM give addition mass while toluene and n-hexane give reduction mass in the
blend. IRM is oil while toluene and n-hexane is a hydrocarbon solvent that has an aromatic and aliphatic chain.
These solvents have different ability to swell or to dissolve the blends.
Figure 2 shows that MBS give the highest swelling index in oil and hydrocarbon solvent while BIIR and
zeolite give almost same swelling index. IRM give the highest swelling index on NBR/EPDM blend. The lower
swelling percentage, the higher solvent resistance of the blend. There was an increase of swelling index until the
fifth day, then the swelling index decreased. This indicates that the more time, the more solvents diffused in the
rubber molecule. But at certain times the rubber molecule is saturated so that it can not absorb the solvent and
release it. While the hydrocarbon solvent, toluene, and n-hexane, gives no significant swelling index differences
from the first day until the fifth day. Toluene and n-hexane give lower swelling index than IRM, and toluene gives
higher swelling index than n-hexane. It is in accordance with the study by the previous study that gives a result that
the absorption of aromatic solvent is higher than aliphatic solvents. EPDM also has a good swelling resistance in
toluene and n-hexane [21].

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 3 0

2 0
N E B
1 0 N E Z

0 N E M
0 2 4 6
D ay

( a)
0
0 2 4 6
-1 0 N E B

-2 0 N E Z
N E M
-3 0
D ay

( b)
0
-4 0 2 4 6

-8 N E B
-1 2 N E Z
-1 6 N E M
-2 0
D ay

(c )

FIGURE 2. Swelling index of NBR/EPDM blend at (a) IRM, (b) toluene, (c) n-hexane as the solvent

CONCLUSION
The blending of NBR/EPDM with different compatibilizer give different thermogravimetry and swelling
characteristic. All of the blends have similar thermogravimetric characteristics with two stage of the degradation
process. The first degradation stage occurs at 30-207 ºC and the second stage occurs at 181-517 ºC. The higher
heating rate, the higher peak temperatures and initial temperatures of the second stage. Methyl methacrylate-
butadiene-styrene (MBS) give the highest mass residue after heating until 600 °C (39.63-42.62 %) and give the
lowest swelling index in IRM, toluene, and n-hexane. Bromobutyl rubber (BIIR) give the lowest mass residue
(36.64-38.28 %) and the highest activation energy at each stage (24.71 and 20.78 kJ/mol). Zeolite gives the
thermogravimetry and swelling characteristics between MBS and BIIR. MBS is a suitable compatibilizer for
NBR/EPDM blend to get a good thermal and swelling resistance.

ACKNOWLEDGMENTS
The authors would like to thank the research team and the Center for Leather, Rubber, and Plastics who have helped
and funded this research.

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 REFERENCES

[1] N. Ning, Q. Ma, Y. Zhang, L. Zhang and H. Wu, Polym. Degrad. Stab. 1 8, 102(2014).
[2] H. Nabil, H. Ismail and A. R. Azura, Polym. Test. 385-393, 32 (2013).
[3] H. Ismail and M. Mathialagan, J. Appl. Polym. Sci. 1 8 (2012).
[4] M. E. Tawfik and S.H. El, J. Elastomers Plast. 514 526, 46 (2014).
[5] M. Tavakoli, A.A. Katbab and H. Nazockdast, J. Macromol Sci. 1270 1284, 50 (2011).
[6] S. P. Thomas, E. J. Mathew and C. V. Marykutty, J. Appl. Polym. Sci. 4259 4267, 124 (2011).
[7] E. Ghassemieh, Polym Compos. 1657 1667 (2009).
[8] H. Nabil, H. Ismail and A.R. Azura, Mater. Des. 651 661, 53 (2014).
[9] K. C. Manoj, P. Kumari and G. Unnikrishnan, J. Appl. Polym. Sci. 2654 2662, 120 (2010).
[10] S. Jovanovic, G. Markovic, J. Budinski and M. Marinovic, Composites: Part B 333 340, 45 (2013).
[11] S. A. Al-Ghatani, J. American Sci. 804-809, 7 (2011).
[12] M. Alneamah and M. Almaamori, Int. J. Mater. Chem. 1 3, 5 (2015).
[13] H. E Mayasari, N. M. Setyadewi and A. Yuniari, Pros. Semin. Nas. Kulit, Karet, dan Plast. 111 226, 6
(2017). (in Indonesia)
[14] H. E. Mayasari, A. Yuniari, Maj. Kulit, Karet dan Plast. 125 134, 32 (2016). (in Indonesia)
[15] B. Jankovic, M. Marinovic-Cincovic, V. Jovanovic, S. Samarzija-Jovanovic and G. Markovic,
Thermochimica Acta. 304 312, 543 (2012).
[16] A. Malas and C. K. Das, Polimery 204 211, 58 (2013).
[17] S. Samarzija-Jovanovic, V. Jovanovic, G. Markovic and M. Marinovic-Cincovic, J. Therm. Anal. Calorim.
75 83, 98 (2009).
[18] I. Abed, M. Paraschiv, K. Loubar, F. Zagrouba and M. Tazerout, Bioresour. Technol. 1200 1220, 7 (2012).
[19] N. Kanagathara, M. K. Marchewka and G.Anbalagan, Acta Physica Polonica 1235-1241, 129 (2016).
[20] C. Komalan, K. Elias, K. Thomas, V. Susan and S. Thomas, Polym. Degrad. Stab. 2104-2112, 93 (2008).
[21] K. Ahmed, S. S. Nizami, N. Z. Raza and K. Shirin, Adv. Mater. Phys. Chem. 90 97, 2 (2012).

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