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The Characteristics and Application of Virgin FKM Rubber/Recycled FKM

Rubber Blend

Article  in  Elastomers and Composites · January 2005

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 Journal of Industrial and Engineering Chemistry 19 (2013) 1540–1548

Contents lists available at SciVerse ScienceDirect

Journal of Industrial and Engineering Chemistry

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

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

hydrogenated nitrile rubber
Youn-Gu Yeo a, Hyun-Ho Park b, Chang-Seop Lee a,*
a
Department of Chemistry, Keimyung University, 1000 Shindang-Dong Dalseo-Gu, Daegu, 704-701 Republic of Korea
b
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 A B S T R A C T

Article history: In this study, the physical and chemical characteristics of a rubber blend of fluorocarbon rubber (FKM)
Received 4 July 2012 and hydrogenated Nitrile Butadiene rubber (HNBR) were investigated based on the blend ratio for the
Accepted 18 January 2013 purpose improving thermal resistance of HNBR and the low-temperature resistance of FKM. The blended
Available online 4 February 2013
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
Keywords: basic physical properties than those of the materials without the agent. This result agreed with a
FKM
scanning electron microscopy image. The thermal properties of the blended materials based on the FKM
HNBR
and HNBR blend ratio were studied by Thermo Gravimetric Analysis (TGA) and differential scanning
Blend
Low-temperature resistance calorimetry (DSC). The TGA results showed improved heat resistance characteristics for the blended
Compatibilizer materials than those of the HNBR materials. The DSC results also showed improved characteristics of low
temperature resistance with increasing HNBR contents.
ß 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

1. Introduction mixing by the mechanical blend is high enough to prevent phase

separation.
Fluorocarbon rubber (FKM) and hydrogenated Nitrile Butadiene FKM is also known as Viton rubber of Dupont. It is made by
rubber (HNBR) are mainly used for packing and O-rings in car typical emulsion polymerization and by copolymerization with
engines. FKM materials have excellent heat, chemical, ozone, and fluroroethylene and fluoropropylene. Generally, high molecular
fuel resistance but have weak low-temperature resistance. weight compounds with high fluorine levels are very stable and
Therefore, it is doubtful if FKM and HNBR materials would have a higher C–F synthetic intensity than C–H synthesis. It is very
maintain their quality when a car was operated under ultra high or expensive, but the rubber is very durable. It is mainly used in
low temperatures. We examined the reforming characteristics special areas such as military machines, advanced industrial
based on the blending method to complement the individual machines, and satellites. Dupont, 3 M in the US and DAIKIN in
weaknesses of FKM and HNBR. Japan are some representative manufacturers [10,11].
There are mainly three reasons to blend or mix rubber. It is to HNBR is made by conducting a selective and controlled
improve the mechanical properties and machinability of raw hydrogenated reaction with NBR. A highly saturated methylene
rubber and to reduces the price of the compound. There are one or main chain is excellent for heat resistance and ozone resistance,
more defects in every rubber type, and to blend other rubber is a and the nitrile is oil and fuel resistant. As a result of the
method to achieve an optimal condition [1,2]. Rubber blend hydrogenated reaction, heat and ozone resistance increase with
methods include a latex blend, a solution blend, a mechanical further hydrogen addition. Two types of polymers are commer-
blend, a mechano-chemical blend, and a powder type rubber blend cially usable based on the hydrogenation reaction. One is an almost
[3–5]. The mechanical blend is the most widely used method to saturated type which is cross-linked only with peroxides, as the
manufacture rubber in industry. Although two high molecular original double bonds comprise 1%. The other is to maintain a
materials may not be compatible, a blend of micro homogeneity high rate of double bonds (5–10%) vulcanized by peroxides or
and useful characteristics can be generated if the viscosity after 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
* Corresponding author. Tel.: +82 53 580 5192; fax: +82 53 588 3408. HNBR increases, swelling of mineral oils decreases. But, the loss
E-mail address: surfkm@kmu.ac.kr (C.-S. Lee). of low-temperature flexibility over ordinary NBR is extremely low.

1226-086X/$ – see front matter ß 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) 1540–1548 1541

Table 1 Table 2
Recipe for the fluorocarbon rubber (FKM) and hydrogenated acrilonitrile-butadiene Recipe for the fluorocarbon rubber (FKM) and hydrogenated nitrile-butadiene
rubber (HNBR) blends (test 1). rubber (HNBR) blends (test 2).

Recipe No. a b c d e f Recipe No. c-1 c-2 d-1 d-2

(100/0) (80/20) (60/40) (40–60) (20/80) (0/100) (60/40) (60/40) (40/60) (40/60)

G-902 (FKM) 100 80 60 40 20 0 G-902 (FKM) 60 60 40 40

Zet 2010 (HNBR) 0 20 40 60 90 100 Zet 2010 (HNBR) 40 40 60 60
ZnO 5 5 5 5 5 4 ZnO 5 5 5 5
Perkadox 14-40 4 4 4 4 4 4 Perkadox 14-40 4 4 4 4
TAIC 50 3 3 3 3 3 3 TAIC 50 3 3 3 3
KBM503 2 2 2 2
Total 112 112 112 112 112 112
VN2 15 15

Total 114 129 114 129

This means that an HNBR product with high nitrile NBR can be used
to optimize oil resistance and low-temperature flexibility.
In a study on the phase separation structure of the FKM/HNBR a phase-dissolution by Differential Scanning Calorimetry (DSC)
blend by Hirano et al. [6], atomic force microscopy [7] and and Dynamic Mechanical Thermal Analyzer measurements. As
Transmission Electron Microscopy (TEM) [8] were employed in a such, there are resources on the FKM and HNBR blend, but no
blend analysis and resulted in a phase separation phenomenon at studies on phase-dissolution of the FKM/HNBR blend. According-
the FKM/HNBR ratio of 30:70. Kader and Bhowmick, in their study ly, we examined the FKM/HNBR blend characteristics using a
on a commercial blend of acrylate rubber and FKM [9], reported compatibilizer.

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

Fig. 2. The cure graph of the fluorocarbon rubber (FKM) and hydrogenated acrilonitrile-butadiene rubber (HNBR) blends (test 2).
1542 Y.-G. Yeo et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 1540–1548

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

Contents a b c d e f
(100/0) (80/20) (60/40) (40/60) (20/80) (0/100)

ODR (180 8C  6 min) Tmax 31.8 37.6 36.6 32.6 27.6 23.4
Tmin 2.3 2.2 3.7 3.9 4.3 4.5
tc50 (s) 159 121 143 164 175 184
ts2 (s) 74 77 83 85 87 92

Contents c-1 c-2 d-1 d-2

(60/40) (60/40) (40/60) (40/60)

ODR (180 8C  6 min) Tmax 15.0 32.7 15.0 39.7

Tmin 3.8 6.0 3.6 6.3
tc50 (s) 222 203 240 201
ts2 (s) 142 89 160 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 fluorocarbon rubber (FKM) and hydrogenated
nitrile-butadiene rubber (HNBR) blends by differential scanning calorimetry.

Recipe No a b c d e f

Tg(8C) 5.96 4.83 27.02 27.03 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 Fig. 4. Basic properties of the fluorocarbon rubber (FKM) and hydrogenated
raw rubbers. As there is a blend effect by selecting the same acrilonitrile-butadiene rubber (HNBR) blends (test 2).
crosslinking type of two materials, material which is peroxide
cross linking type was selected to improve the compressed samples. Compatibilizer (KBM503) was used to enhance the blend
permanent shortening ratio and heat resistance compared with effect of FKM (Table 2).
that of the sulfur cross linking type.
The cross linking assisting agents were ZnO (Hanil Chemical, 2.3. Specimen preparation
Siheung City, Korea), and the cross linking agent was Perkadox 14-
40 (di-(2-t-butylperoxy-isopropyl) benzene (Akzo Nobel, Amster- Specimens were blended with a mechanical blending method.
dam, The Netherlands), the co-crosslinking agent was TAIC 50 (co- Mastication was conducted with the FKM and HNBR raw materials
agent, Triallyl isocyanulate, Tokyo, Japan), the reinforcing agent at 60 8C for 5 min, respectively using an open roll mill (8 in. open
was VN2 (Silica, Degussa, Germany), and the compatibilizer was roll mill, Hyunjin). Separately masticated FKM raw material and
KBM503 (g-methacryloyloxypropyl-trimethoxy silane, Shin-Etsu, HNBR material were blended at 60 8C for 5 min, the additives were
Tokyo, Japan). 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
2.2. Compounding compressed specimen were prepared at regular temperature
(160 8C) and pressure (140 kg/cm2) to measure the properties of
Basic subsidiary material was used for the compounding ratio in the blended final master batch.
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 first compounded

Fig. 3. Basic properties of fluorocarbon rubber (FKM) and hydrogenated nitrile- Fig. 5. Change in hardness, tensile strength, and elongation after heating at 150 8C
butadiene rubber (HNBR) blends (test 1). for 70 h (test 1).
 Y.-G. Yeo et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 1540–1548 1543

products with a wave number domain of 4000–650 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 (300–600 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 fluorocarbon rubber (FKM) and hydrogenated nitrile-
butadiene 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 reflectance
(PerkinElmer Spectrum GX System, Waltham, MA, USA) apparatus
was used to measure the change in specific pear area of the blended

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

Fig. 8. Oil resistance of fluorocarbon rubber (FKM) and hydrogenated nitrile- FKM and hydrogenated nitrile-butadiene rubber (HNBR) blend with varying
butadiene rubber (HNBR) blends (test 2). compositions.
1544 Y.-G. Yeo et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 1540–1548

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) 1540–1548 1545

the phase separation and diversity of each raw material at 1000 3.2. Basic properties
in comparison with a blended specimen.
Tensile strength decreased as HNBR blend rate increased. But,
when specimens C and D with C-1 and D-1 were compared, C-1
3. Results and discussion and D-1 had higher increases in tensile strength and elongation
than those of C and D respectively. An optimal blending effect
3.1. Vulcanization characteristics occurred with FKM and HNBR by using a compatibilizer such as
KBM503 (Silane). Adding reinforcing agents (VN2 and silica)
As the HNBR blend rate was increased, vulcanization speed and controlled the hardness, tensile strength, and elongation proper-
scorch time decreased, because it created a curve with a continual ties Figs. 3 and 4.
increase (tc90 as a normal vulcanization time is meaningless with
no consistency). Thus in this experiment, tc50 was adopted as the 3.3. Heat resistance
blended specimen vulcanization character comparative data. As a
result, as HNBR blend rate was increased, the tc50 tended to be The properties were measured after a heat resistance test
delayed, demonstrating that the tc50 was influenced by the and compared with basic properties to test the heat resistance
vulcanization character of the HNBR Figs. 1 and 2, Tables 3 and 4.

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.
1546 Y.-G. Yeo et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 1540–1548

Fig. 13. Scanning electron micrographs of fluorocarbon 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. 3.5. FTIR
Tensile strength and elongation percentage increased sharply
with 80 phr of HNBR blend content. As a result, a blend effect A change in the functional absorbing peak per specimen based
was shown for up to a 60 phr of HNBR content. Specimens with on blending ratio was observed. Fig. 9 shows that the absorbing
a reinforcing agent had better heat resistance than those peak of HNBR nitrile (–CN) (about 2236 cm 1) became sharp when
without. the proportion of HNBR increased. The absorption peak at about
2925 cm 1 and that at about 2856 cm 1 showed asymmetric
3.4. Oil and fuel resistance flexible vibration and symmetrical flexible vibration at –CH. The
absorption peak at 723 cm 1 was shown by the –CH2 group.
To determine the fluid characteristics of the blended The FKM absorption peak of the –CF link – (about 1128 cm 1)
specimen, the change in hardness and volume with ASTM No became weak along with the increase in HNBR rate. The peak
3. Oil and fuel D were compared at 150 8C for 70 h and at a became sharp when samples were moved from c-1 to c-2 and d-1
room temperature for 70 h. The change in hardness and to d-2 at about 1100 cm 1 where the absorption peak was by FKM–
volume increased as HNBR content increased, demonstrating CF. This result probably occurred because of the link of Si–O–Si to
that the fluid characteristics of FKM were better than those of silica (VN2) Figs. 10–12.
HNBR. Better hardness and volume changes were observed
when HNBR content was 60 phr rather than when it was 40 phr. 3.6. TGA
This result demonstrated that a 40:60 blend ratio between FKM
and HNBR resulted in a better blend effect than that of 60:40 The pyrolysis temperature of the polymer was measured based
Figs. 5–8. on the blending rate. The pyrolysis temperature of FKM (100 phr)
 Y.-G. Yeo et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 1540–1548 1547

Fig. 14. Scanning electron micrographs of fluorocarbon 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 than that of HNBR. The FKM and HNBR blend effect developed by
blended specimens (b), (c), (d) and (e), HNBR pyrolyzed adding a compatibilizer. Adding a reinforcing agent (VN2)
at > 419 8C, whereas FKM pyrolyzed at > 545.2 8C. This demon- increased dispersion than it was not added.
strates that the FKM and HNBR blended specimen (b–e) had
improved heat resistance than that of the HNBR alone (f). 4. Conclusions

3.7. DSC We prepared specimens according to the FKM and HNBR

blend ratio by means of a mechanical blending method and
Tg was measured according to the change in HNBR content. Tg examined the basic properties, heat resistance, oil resistance
decreased and low temperature character improved with an and fuel resistance, as well as chemical characteristics (FTIR,
increase in HNBR content. In particular, Tg decreased sharply with TGA, DSC, and SEM). As a result, hardness and tensile strength
the 60:40 blend, because of the synergistic effect as HNBR blend decreased along with increasing HNBR contents. Tensile
content was increased. strength and elongation increased by adding a compatibilizer
(KBM503), which contributed to increase the blend effect.
3.8. Surface dispersion Suitable basic properties were obtained by controlling the
amount of a reinforcing agent. Heat resistance increased along
Figs. 13 and 14 show the surface dispersion image at 1000 with increasing HNBR contents. A synergistic effect of heat
according to changes in the HNBR blend content. Fig. 13 shows a resistance was achieved by blending FKM and HNBR, and fluid
phase separation phenomenon in the blended sample, whereas characteristics (oil resistance and fuel resistance) are also same
Fig. 14 does not, because the surface tension of FKM was higher Heat resistance.
1548 Y.-G. Yeo et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 1540–1548

The FTIR analysis revealed changes in specific absorption peaks References

with each blend ratio. The TGA analysis showed that blended
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