Journal of Industrial and Engineering Chemistry 19 (2013) 15401548

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

A study on the characteristics of a rubber blend of uorocarbon rubber and

hydrogenated nitrile rubber
Youn-Gu Yeo a, Hyun-Ho Park b, Chang-Seop Lee a,*
a
b

Department of Chemistry, Keimyung University, 1000 Shindang-Dong Dalseo-Gu, Daegu, 704-701 Republic of Korea
Hwaseung Material, Ltd., 147-1 Gyo-Dong Yangsan-Gun, Kyungnam, 626-210 Republic of Korea

A R T I C L E I N F O

Article history:
Received 4 July 2012
Accepted 18 January 2013
Available online 4 February 2013
Keywords:
FKM
HNBR
Blend
Low-temperature resistance
Compatibilizer

A B S T R A C T

In this study, the physical and chemical characteristics of a rubber blend of uorocarbon rubber (FKM)
and hydrogenated Nitrile Butadiene rubber (HNBR) were investigated based on the blend ratio for the
purpose improving thermal resistance of HNBR and the low-temperature resistance of FKM. The blended
FKM and HNBR materials showed better heat resistance, oil resistance, and fuel resistance than those of
the 100 phr HNBR materials. Blended materials with added compatibilizer (KBM503) showed improved
basic physical properties than those of the materials without the agent. This result agreed with a
scanning electron microscopy image. The thermal properties of the blended materials based on the FKM
and HNBR blend ratio were studied by Thermo Gravimetric Analysis (TGA) and differential scanning
calorimetry (DSC). The TGA results showed improved heat resistance characteristics for the blended
materials than those of the HNBR materials. The DSC results also showed improved characteristics of low
temperature resistance with increasing HNBR contents.
2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

1. Introduction
Fluorocarbon rubber (FKM) and hydrogenated Nitrile Butadiene
rubber (HNBR) are mainly used for packing and O-rings in car
engines. FKM materials have excellent heat, chemical, ozone, and
fuel resistance but have weak low-temperature resistance.
Therefore, it is doubtful if FKM and HNBR materials would
maintain their quality when a car was operated under ultra high or
low temperatures. We examined the reforming characteristics
based on the blending method to complement the individual
weaknesses of FKM and HNBR.
There are mainly three reasons to blend or mix rubber. It is to
improve the mechanical properties and machinability of raw
rubber and to reduces the price of the compound. There are one or
more defects in every rubber type, and to blend other rubber is a
method to achieve an optimal condition [1,2]. Rubber blend
methods include a latex blend, a solution blend, a mechanical
blend, a mechano-chemical blend, and a powder type rubber blend
[35]. The mechanical blend is the most widely used method to
manufacture rubber in industry. Although two high molecular
materials may not be compatible, a blend of micro homogeneity
and useful characteristics can be generated if the viscosity after

* Corresponding author. Tel.: +82 53 580 5192; fax: +82 53 588 3408.
E-mail address: surfkm@kmu.ac.kr (C.-S. Lee).

mixing by the mechanical blend is high enough to prevent phase

separation.
FKM is also known as Viton rubber of Dupont. It is made by
typical emulsion polymerization and by copolymerization with
uroroethylene and uoropropylene. Generally, high molecular
weight compounds with high uorine levels are very stable and
have a higher CF synthetic intensity than CH synthesis. It is very
expensive, but the rubber is very durable. It is mainly used in
special areas such as military machines, advanced industrial
machines, and satellites. Dupont, 3 M in the US and DAIKIN in
Japan are some representative manufacturers [10,11].
HNBR is made by conducting a selective and controlled
hydrogenated reaction with NBR. A highly saturated methylene
main chain is excellent for heat resistance and ozone resistance,
and the nitrile is oil and fuel resistant. As a result of the
hydrogenated reaction, heat and ozone resistance increase with
further hydrogen addition. Two types of polymers are commercially usable based on the hydrogenation reaction. One is an almost
saturated type which is cross-linked only with peroxides, as the
original double bonds comprise 1%. The other is to maintain a
high rate of double bonds (510%) vulcanized by peroxides or
sulfur [12].
The best properties can be obtained using a hydrogenated
rubber which has oil resistance like NBR and heat and ozone
resistance like ethylene-propylene-diene. As the nitrile content of
HNBR increases, swelling of mineral oils decreases. But, the loss
of low-temperature exibility over ordinary NBR is extremely low.

1226-086X/$ see front matter 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2013.01.021

Y.-G. Yeo et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 15401548
Table 1
Recipe for the uorocarbon rubber (FKM) and hydrogenated acrilonitrile-butadiene
rubber (HNBR) blends (test 1).
Recipe No.

(100/0)

(80/20)

(60/40)

(4060)

(20/80)

(0/100)

G-902 (FKM)
Zet 2010 (HNBR)
ZnO
Perkadox 14-40
TAIC 50

100
0
5
4
3

80
20
5
4
3

60
40
5
4
3

40
60
5
4
3

20
90
5
4
3

0
100
4
4
3

Total

112

112

112

112

112

112

Table 2
Recipe for the uorocarbon rubber (FKM) and hydrogenated nitrile-butadiene
rubber (HNBR) blends (test 2).
Recipe No.

G-902 (FKM)
Zet 2010 (HNBR)
ZnO
Perkadox 14-40
TAIC 50
KBM503
VN2
Total

This means that an HNBR product with high nitrile NBR can be used
to optimize oil resistance and low-temperature exibility.
In a study on the phase separation structure of the FKM/HNBR
blend by Hirano et al. [6], atomic force microscopy [7] and
Transmission Electron Microscopy (TEM) [8] were employed in a
blend analysis and resulted in a phase separation phenomenon at
the FKM/HNBR ratio of 30:70. Kader and Bhowmick, in their study
on a commercial blend of acrylate rubber and FKM [9], reported

1541

c-1

c-2

d-1

d-2

(60/40)

(60/40)

(40/60)

(40/60)

60
40
5
4
3
2

60
40
5
4
3
2
15

40
60
5
4
3
2

40
60
5
4
3
2
15

114

129

114

129

a phase-dissolution by Differential Scanning Calorimetry (DSC)

and Dynamic Mechanical Thermal Analyzer measurements. As
such, there are resources on the FKM and HNBR blend, but no
studies on phase-dissolution of the FKM/HNBR blend. Accordingly, we examined the FKM/HNBR blend characteristics using a
compatibilizer.

Fig. 1. The cure graph of the uorocarbon rubber (FKM) and hydrogenated nitrile-butadiene rubber (HNBR) blends (test 1).

Fig. 2. The cure graph of the uorocarbon rubber (FKM) and hydrogenated acrilonitrile-butadiene rubber (HNBR) blends (test 2).

Y.-G. Yeo et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 15401548

1542

Table 3
Cure characteristics of the uorocarbon rubber (FKM) and hydrogenated acrilonitrile-butadiene rubber (HNBR) blends.
Contents

ODR (180 8C  6 min)

Tmax
Tmin
tc50 (s)
ts2 (s)

(100/0)

(80/20)

(60/40)

(40/60)

(20/80)

(0/100)

31.8
2.3
159
74

37.6
2.2
121
77

36.6
3.7
143
83

32.6
3.9
164
85

27.6
4.3
175
87

23.4
4.5
184
92

Contents

ODR (180 8C  6 min)

Tmax
Tmin
tc50 (s)
ts2 (s)

c-1

c-2

d-1

d-2

(60/40)

(60/40)

(40/60)

(40/60)

15.0
3.8
222
142

32.7
6.0
203
89

15.0
3.6
240
160

39.7
6.3
201
89

Tmax: maximum torque, Tmin: minimum torque, tc50: 50% curing time, ts2: Scorch Time (i) Test 1.
Tmax: maximum torque, Tmin: minimum torque, tc50: 50% curing time, ts2: Scorch Time (ii) Test 2.

Table 4
Glass transition temperature (Tg) of uorocarbon rubber (FKM) and hydrogenated
nitrile-butadiene rubber (HNBR) blends by differential scanning calorimetry.
Recipe No

Tg(8C)

b
5.96

c
4.83

d
27.02

e
27.03

f
27.03

27.75

2. Experimental
2.1. Materials
The following materials were used to manufacture the FKM/
HNBR blend in this study. FKM rubber (G-902, DAKIN, Osaka,
Japan) and HNBR rubber (Zetpol-2010, JEON, Japan) were used as
raw rubbers. As there is a blend effect by selecting the same
crosslinking type of two materials, material which is peroxide
cross linking type was selected to improve the compressed
permanent shortening ratio and heat resistance compared with
that of the sulfur cross linking type.
The cross linking assisting agents were ZnO (Hanil Chemical,
Siheung City, Korea), and the cross linking agent was Perkadox 1440 (di-(2-t-butylperoxy-isopropyl) benzene (Akzo Nobel, Amsterdam, The Netherlands), the co-crosslinking agent was TAIC 50 (coagent, Triallyl isocyanulate, Tokyo, Japan), the reinforcing agent
was VN2 (Silica, Degussa, Germany), and the compatibilizer was
KBM503 (g-methacryloyloxypropyl-trimethoxy silane, Shin-Etsu,
Tokyo, Japan).
2.2. Compounding
Basic subsidiary material was used for the compounding ratio in
the FKM/HNBR blend according to the blend ratio at initial
compounding (Table 1), and a reinforcing agent (VN2) was used to
increase the basic properties of c and d in the rst compounded

Fig. 3. Basic properties of uorocarbon rubber (FKM) and hydrogenated nitrilebutadiene rubber (HNBR) blends (test 1).

Fig. 4. Basic properties of the uorocarbon rubber (FKM) and hydrogenated

acrilonitrile-butadiene rubber (HNBR) blends (test 2).

samples. Compatibilizer (KBM503) was used to enhance the blend

effect of FKM (Table 2).
2.3. Specimen preparation
Specimens were blended with a mechanical blending method.
Mastication was conducted with the FKM and HNBR raw materials
at 60 8C for 5 min, respectively using an open roll mill (8 in. open
roll mill, Hyunjin). Separately masticated FKM raw material and
HNBR material were blended at 60 8C for 5 min, the additives were
supplied, and the compound was masticated at 60 8C for 15 min to
produce a sheet. A plain specimen (dumbbell type No. 3) and a
compressed specimen were prepared at regular temperature
(160 8C) and pressure (140 kg/cm2) to measure the properties of
the blended nal master batch.

Fig. 5. Change in hardness, tensile strength, and elongation after heating at 150 8C
for 70 h (test 1).

Y.-G. Yeo et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 15401548

1543

products with a wave number domain of 4000650 cm 1. The loss

of weight according to the temperature increase at 20 8C/min using
Thermo Gravimetric Analysis (TGA, PerkinElmer Pyris 1 TGA) was
observed by calculating pyrolysis temperature on the relevant
rubber area (300600 8C) to measure the change in heat resistance
of the blended specimen.
Differential Scanning Calorimetry (DSC; PerkinElmer) was used
to determine the low-temperature characteristics and to measure
glass transition temperature (Tg) with a temperature increase of
10 8C/min in the
40 to 200 8C range. Scanning Electron
Microscopy (SEM; JSM-6100, Tokyo, Japan) was used to determine

Fig. 6. Change in hardness, tensile strength and elongation after heating at 150 8C
for 70 h (test 2).

Fig. 7. Oil resistance of the uorocarbon rubber (FKM) and hydrogenated nitrilebutadiene rubber (HNBR) blends (test 1).

2.4. Characterization
Temperature was set at 180 8C in an oscillating disk rheometer
to examine vulcanization of the blended sample (ODR 2000,
Kunwha Engineering, Seoul, Korea) and to measure maximum and
minimum torques, scorch times for the initial vulcanizing time of
the rubber (ts2, s), and optimal vulcanization time (tc90, s).
Tensile strength, elongation percentage, and modulus were
measured at room temperature and a speed of 500 mm/min. The
hardness test was carried out using a spring shape A type hardness
tester (JISA, Tokyo, Japan).
The heat resistance properties of the vulcanized rubber was
measured after heating at 150 8C for 70 h. Oil resistance
was measured after immersing in ASTM No. 3 at 150 8C for 70 h.
Fuel resistance was measured after immersing in FUEL D
(isooctane (4):toluene (6)) at a room temperature for 70 hr. in
terms of its hardness, tensile characteristics, and volume changes.
A Fourier transform infrared-attenuated total reectance
(PerkinElmer Spectrum GX System, Waltham, MA, USA) apparatus
was used to measure the change in specic pear area of the blended

Fig. 8. Oil resistance of uorocarbon rubber (FKM) and hydrogenated nitrilebutadiene rubber (HNBR) blends (test 2).

Fig. 9. Fourier-transform infrared (FTIR) spectra of uorocarbon rubber (FKM) and

FKM and hydrogenated nitrile-butadiene rubber (HNBR) blend with varying
compositions.

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Y.-G. Yeo et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 15401548

Fig. 10. FT-IR spectra of FKM and FKM/HNBR blend with varying composition: (c-1) sample (c) + KBM503, (c-2) sample (c) + KBM503,VN2, (d-1) sample (d) + KBM503, (d-2)
sample (d) + KBM503,VN2.

Fig. 11. TGA of FKM and FKM/HNBR blend with varying composition: (a) 100% FKM, (b) 80/20 FKM/HNBR, (c) 60/40 FKM/HNBR, (d) 40/60 FKM/HNBR, (e) 20/80 FKM/HNBR,
(f) 100% HNBR.

Y.-G. Yeo et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 15401548

the phase separation and diversity of each raw material at 1000

in comparison with a blended specimen.

3. Results and discussion

3.1. Vulcanization characteristics
As the HNBR blend rate was increased, vulcanization speed and
scorch time decreased, because it created a curve with a continual
increase (tc90 as a normal vulcanization time is meaningless with
no consistency). Thus in this experiment, tc50 was adopted as the
blended specimen vulcanization character comparative data. As a
result, as HNBR blend rate was increased, the tc50 tended to be
delayed, demonstrating that the tc50 was inuenced by the
vulcanization character of the HNBR Figs. 1 and 2, Tables 3 and 4.

1545

3.2. Basic properties

Tensile strength decreased as HNBR blend rate increased. But,
when specimens C and D with C-1 and D-1 were compared, C-1
and D-1 had higher increases in tensile strength and elongation
than those of C and D respectively. An optimal blending effect
occurred with FKM and HNBR by using a compatibilizer such as
KBM503 (Silane). Adding reinforcing agents (VN2 and silica)
controlled the hardness, tensile strength, and elongation properties Figs. 3 and 4.
3.3. Heat resistance
The properties were measured after a heat resistance test
and compared with basic properties to test the heat resistance

Fig. 12. DSC thermogram of FKM and FKM/HNBR blend with varying composition: (a) 100% FKM, (b) 80/20(w/w) FKM/HNBR, (c) 60/40 FKM/HNBR, (d) 40/60 FKM/HNBR,
(e) 20/80 FKM/HNBR, (f) 100% HNBR.

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Y.-G. Yeo et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 15401548

Fig. 13. Scanning electron micrographs of uorocarbon rubber (FKM) and FKM and hydrogenated acrilonitrile-butadiene rubber blends of varying compositions; (a) 100%
FKM, (b) 80/20 FKM/HNBR, (c) 60/40 FKM/HNBR, (d) 40/60 FKM/HNBR, (e) 20/80 FKM/HNBR, (f) 100% HNBR.

of rubber samples by the FKM and HNBR blend percentage.

Tensile strength and elongation percentage increased sharply
with 80 phr of HNBR blend content. As a result, a blend effect
was shown for up to a 60 phr of HNBR content. Specimens with
a reinforcing agent had better heat resistance than those
without.
3.4. Oil and fuel resistance
To determine the uid characteristics of the blended
specimen, the change in hardness and volume with ASTM No
3. Oil and fuel D were compared at 150 8C for 70 h and at a
room temperature for 70 h. The change in hardness and
volume increased as HNBR content increased, demonstrating
that the uid characteristics of FKM were better than those of
HNBR. Better hardness and volume changes were observed
when HNBR content was 60 phr rather than when it was 40 phr.
This result demonstrated that a 40:60 blend ratio between FKM
and HNBR resulted in a better blend effect than that of 60:40
Figs. 58.

3.5. FTIR
A change in the functional absorbing peak per specimen based
on blending ratio was observed. Fig. 9 shows that the absorbing
peak of HNBR nitrile (CN) (about 2236 cm 1) became sharp when
the proportion of HNBR increased. The absorption peak at about
2925 cm 1 and that at about 2856 cm 1 showed asymmetric
exible vibration and symmetrical exible vibration at CH. The
absorption peak at 723 cm 1 was shown by the CH2 group.
The FKM absorption peak of the CF link (about 1128 cm 1)
became weak along with the increase in HNBR rate. The peak
became sharp when samples were moved from c-1 to c-2 and d-1
to d-2 at about 1100 cm 1 where the absorption peak was by FKM
CF. This result probably occurred because of the link of SiOSi to
silica (VN2) Figs. 1012.
3.6. TGA
The pyrolysis temperature of the polymer was measured based
on the blending rate. The pyrolysis temperature of FKM (100 phr)

Y.-G. Yeo et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 15401548

1547

Fig. 14. Scanning electron micrographs of uorocarbon rubber (FKM) and FKM and hydrogenated acrilonitrile-butadiene rubber blend of varying compositions; (c) 60/40
FKM/HNBR, (d) 40/60 FKM/HNBR, (c-1) sample (c) + KBM503, (c-2) sample (c) + KBM503,VN2, (d-1) sample (d) + KBM503, (d-2) sample (d) + KBM503,VN2.

was 511.5 8C, whereas that of HNBR (100 phr) was 406.98 8C. In the
blended specimens (b), (c), (d) and (e), HNBR pyrolyzed
at > 419 8C, whereas FKM pyrolyzed at > 545.2 8C. This demonstrates that the FKM and HNBR blended specimen (be) had
improved heat resistance than that of the HNBR alone (f).

than that of HNBR. The FKM and HNBR blend effect developed by
adding a compatibilizer. Adding a reinforcing agent (VN2)
increased dispersion than it was not added.

3.7. DSC

We prepared specimens according to the FKM and HNBR

blend ratio by means of a mechanical blending method and
examined the basic properties, heat resistance, oil resistance
and fuel resistance, as well as chemical characteristics (FTIR,
TGA, DSC, and SEM). As a result, hardness and tensile strength
decreased along with increasing HNBR contents. Tensile
strength and elongation increased by adding a compatibilizer
(KBM503), which contributed to increase the blend effect.
Suitable basic properties were obtained by controlling the
amount of a reinforcing agent. Heat resistance increased along
with increasing HNBR contents. A synergistic effect of heat
resistance was achieved by blending FKM and HNBR, and uid
characteristics (oil resistance and fuel resistance) are also same
Heat resistance.

Tg was measured according to the change in HNBR content. Tg

decreased and low temperature character improved with an
increase in HNBR content. In particular, Tg decreased sharply with
the 60:40 blend, because of the synergistic effect as HNBR blend
content was increased.
3.8. Surface dispersion
Figs. 13 and 14 show the surface dispersion image at 1000
according to changes in the HNBR blend content. Fig. 13 shows a
phase separation phenomenon in the blended sample, whereas
Fig. 14 does not, because the surface tension of FKM was higher

4. Conclusions

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Y.-G. Yeo et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 15401548

The FTIR analysis revealed changes in specic absorption peaks

with each blend ratio. The TGA analysis showed that blended
materials had increased heat resistance compared with that of the
single materials alone. The DSC analysis revealed that when HNBR
content was increased the low-temperature characteristics increased sharply (from 40 phr). The SEM observations showed that
when compatibilizer (KBM503) was used, it prevented the phase
separating phenomenon and increased dispersion, which was
enhanced by a reinforcing agent (VN2).
Acknowledgements
This research was nancially supported by the Ministry of
Education, Science Technology (MEST) and National Research
Foundation of Korea(NRF) through the Human Resource Training
Project for Regional Innovation

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