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Wax  Ozone-degradation  Rubber 
Bloom  Thermal contraction
Effect of wax on the ozone resistance of
vulcanized natural rubber (NR) and vul-
canized isoprene rubber (IR) was inves-
tigated by observing crack propagation
of the vulcanized rubbers at 40°C and
-30°C under 50 pphm ozone atmosphe-
re. The ozone exposure test for the vul-
canized rubbers was performed, after
the wax bloomed at 40°C under a strain
of 0.2. The crack propagation of the vul-
canized rubbers was conspicuous at
-30°C, whereas it was little at 40°C. The
crack propagation was related to flaws
in wax layer, which were generated by
cooling at -30°C, after the wax bloomed
at 40°C. It was found that the flaws of
the wax layer, generated at -30°C, was
the origin of the crack propagation of
the vulcanized rubbers.
Geringe Ozonbeständigkeit
von Antiozonwachshaltigem
Isoprenkautschuk unterhalb
der Einfriertemperatur
Wachs  Ozondegradation  Kautschuk 
Ausblühungen  Thermische Kontraktion
Es wurde die Wirkung von Wachs auf
die Ozonbeständigkeit von vulkanisier-
ten Naturkautschuk (NR) und von Isop-
renkautschuk (IR) untersucht, wobei
das Risswachstum des vulkanisierten
Kautschuks bei 40 °C und -30 °C bei
50 pphm ozonhaltiger Atmosphäre be-
obachtet wurde. Der Ozontest erfolgte
für den vulkanisierten Kautschuk, nach-
dem das Wachs bei 40 °C unter einer
Dehnung von 0,2 ausgeblüht war. Das
Risswachstum des vulkanisierten Kaut-
schuks war bei -30 °C auffällig, wobei es
bei 40 °C geringer war. Das Risswachs-
tum stand in Zusammenhang mit De-
fekten in der Wachsschicht, die bei
-30 °C erzeugt wurde, nachdem das
Wachs bei 40 °C ausgeblüht war. Es
wurde festgestellt, dass die Defekte der
bei -30 °C erzeugten Wachsschicht die
Ursache für das Risswachstum am vul-
kanisierten Kautschuk war.
Figures and Tables:
By a kind approval of the authors.
32 KGK · 03 2018
Ozone-Resistivity of Isoprene
Rubber mixed with a Wax as an
Antiozonant at below Freezing
Introduction
Wax is known to have an ability to pre-
vent ozone-degradation of vulcanized
rubber products [1-5]. It may, thus, pro-
long a lifetime of the products without
deteriorations and serious troubles [6-9].
A plausible effect of the wax as an antio-
zonant is schematically illustrated in Fig-
ure 1. First, the wax in the rubber prod-
ucts migrates to the surface due to active
molecular movement of the rubber. Sec-
ond, a wax layer is formed on the surface
of the rubber products due to blooming.
The resulting wax layer may protect the
rubber products against ozone; that is, it
prevents a reaction of the rubber with
ozone as a barrier layer [10-12]. In prac-
tice, the ozone resistivity of the rubber
products under static condition at ambi-
ent temperature is improved by forming
the wax layer on their surfaces.
However, recently, some troubles with
cracks on a rubber bearing were reported
in winter season, even though the rubber
bearing was completely covered with
thick wax layer [13]. The cracks were at-
tributed to the ozone degradation at low
temperature due to high latitude in Ja-
pan. It should not occur if the wax layer
had protected the rubber bearing. In this
regard, the reported cracks at low tem-
perature were distinguished from ordi-
nary cracks due to ozone degradation; in
general, the lower the temperature, the
slower the ozone degradation [14-16].
For instance, in the case of an ordinary
ozone degradation of vulcanized NBR
(nitrile rubber) without an antiozonant,
a large number of the ozone cracks are
found at 40°C and a little at 0°C, whereas
no crack is found at -30°C.
We, thus, hypothesize that the ozone
cracks are attributed to low temperature
properties of the wax and morphology of
the wax layer on the rubber bearing. In
order to prove the hypothesis, in this
study, an attempt to investigate the
ozone degradation of vulcanized NR
(natural rubber) and vulcanized IR (iso-
prene rubber) was performed under low
temperature condition, which was free
from adhesion, freezing and melting of
ice and snow. Here, we report the mecha-
nism of ozone degradation of vulcanized
NR and vulcanized IR, which were mixed
with a paraffin wax, under low tempera-
ture condition. Aim of this study is to in-
vestigate the effect of wax on the ozone
degradation of vulcanized rubber at 40°C
and -30°C, which are corresponding to
summer season and winter season, re-
spectively.
Experimental
1. Samples
Vulcanized NR sheet used for the actual
rubber bearing and vulcanized IR sheet
as a model were used in this study. The
content of the NR sheet was NR of 62.1
wt%, carbon black of 21.9 wt% and ash
of 4.3 wt% by thermogravimetry accord-
ing to ISO 9924-1 “Rubber and rubber
products - Determination of the compo-
sition of vulcanizates and uncured com-
pounds by thermogravimetry - Part 1:
Butadiene, ethylene-propylene copoly-
mer and terpolymer, isobutene-isoprene,
isoprene and styrene-butadiene rubber”.
The IR formulation is given in Table 1. IR
used was IR2200 purchased from JSR
Corp. Carbon black was Industry Refer-
ence Black (IRB#5, Columbian Chemicals
Co.). Zinc oxide was purchased from
Hakusuitech Co., Ltd. Stearic acid was
Authors
Yuka Iwase, Toru Shindo, Hiroaki
Kondo, Yoshito Ohtake, Saitama,
Seiichi Kawahara, Niigata, Japan
Corresponding Author:
Yuka Iwase
Chemicals Evaluation and
Research Institute Japan
1600 Shimo-takano, Sugito-machi
Kitakatsusika-gun, Saitama, Japan
345-0043
Phone +81-480-37-2601
Fax +81-480-37-2521
E-Mail: iwase-yuka@ceri.jp
www.kgk-rubberpoint.de
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purchased from NOF Corp. Sulfur was

1 Compounding formulation of IR (Unit: phr)
purchased from Hosoi Chemical Industry
Co., Ltd. Accelerator TBBS (N-(tert-Butyl)- Ingredients No.1 No.2 No.3 No.4 No.5
2-benzo- thiazolesulfenamide) and wax Isoprene rubber 100 100 100 100 100
SUNNOC as an antiozonant were pur- Carbon black (IRB*1) 35 35 35 35 35
chased from Ouchi Shinko Chemical In- Zinc oxide 5 5 5 5 5
dustrial Co., Ltd. As for the wax, the Stearic acid 2 2 2 2 2
weight average molecular weight (Mw) Sulfur 2.25 2.25 2.25 2.25 2.25
was 910, the number average molecular Accelerator (TBBS*2) 0.7 0.7 0.7 0.7 0.7
weight (Mn) was 870 and the melting Antiozonant (Wax) 0.0 0.5 1.0 2.0 4.0
point was 73.2°C, in which the molecular *1 Industry Reference Black
weight was measured by size exclusive *2 N-(tert-Butyl)-2-benzothiazolesulfenamide

chromatography consisting of a differen-

tial refractometer detector (RI-101, 1
Showa Denko K. K.), two tandem column
(Shodex GPC KF802.5 + KF801, Showa
Denko K. K.) and HPLC-pump (uf-
3005SZB2, Uniflows Co., Ltd.), and the
melting point was measured by differen-
tial scanning calorimetry (DSC823e, Met-
tler Toledo International Inc.). The Mark-
Houwink parameters used were
K = 1.76 × 104 and α = 0.68 for PS stand-
ard [17]. IR was mixed with those ingre-
dients and 0.0, 0.5, 1.0, 2.0 and 4.0 phr
wax in an open-roll mill (HSU Feng Iron
Fig. 1: Schematically illustration of the effect of the wax as an antiozonant.
Factory) at 80°C. Vulcanization was car-
ried out with a hot press (No.61-034,
Ohtake Kikai Kogyo Co., Ltd.) by pressing 2
the IR compound at 160°C for 8 min.

2. Bloom treatment of wax and ozone

exposure test
The vulcanized rubber was heated at
23°C or 40°C for 72 hours in the presence
of air after stretching at a strain of 0.2 in
order to promote a formation of the wax
layer [18,19]. Hereinafter, it is called
bloom treatment. The amount of
bloomed wax on the surface of the vul-
canized IR was measured by gravimetric
method, that is, just bloomed wax was
physically scraped with a metallic plate
and, then, the amount of bloomed wax
was estimated from a weight loss of the
vulcanized IR. The ozone exposure test
was made with an ozone testing ma-
chine composed of an ozone generator
(OZSD-0008D, Ebara Jitsugyo Co., Ltd), a
ultra-low temperature chamber (MC-
711T, Espec Corp.) and an ozone monitor
(EG-700EIII, Ebara Jitsugyo Co., Ltd.).
Ozone exposure of the vulcanized rubber
was carried out with 50 pphm ozone at
-30, -15, 0, 10, 23 and 40°C for 24 hours
at a strain of 0.2.
3. Degradation assessment for
vulcanized rubber and wax layer
Crack propagation of the vulcanized rub-
ber was observed by digital microscopy
(VHX-2000, Keyence Corp.). Surface of
Fig. 2: Digital microscope images of the test piece of the rubber bearing, exposed with
ozone at (a) 40°C and (b) -30°C (20 magnifications).
the wax layer was observed by scanning
electron microscopy (SEM, JSM-5610LV,
JEOL Ltd.). Thermal contraction coeffi-
cient of a wax and a rubber was meas-
ured by thermomechanical analysis
(TMA, TMA/SDTA 841e, Mettler Toledo
Inc.) at temperature between 23°C and
-30°C. The contraction percentage of wax
and rubber was determined by the fol-
lowing equation.
𝑚𝑚0 − 𝑚𝑚1
∆C = × 100
𝑚𝑚0
where ΔC is the contraction percentage,
m0 is the thickness of the test piece at
23°C and m1 is the thickness of the test
piece at measuring temperature, respec-
tively.
Results and discussion
Figure 2 shows digital microscope imag-
es for the test piece of the rubber bear-
ing, exposed with ozone at 40°C and
-30°C. Ozone crack did not appear at
40°C, whereas it appeared at -30°C. This
implies that the test piece was not dam-
aged with ozone at 40°C, whereas it was
significantly damaged at -30°C. Thus, we
found that the ozone cracks of the rub-
ber bearing generated at low tempera-
ture, which was distinguished from the
ordinary cracks due to the ozone degra-
dation [14-16]. In order to understand
the reason why the ozone cracks of the
rubber bearing generated at low tem-
perature, the ozone degradation of vul-
canized IR as a model was investigated
with respect to the amount of wax, tem-

www.kgk-rubberpoint.de KGK · 03 2018 33

 PRÜFEN UND MESSEN
TESTING AND MEASURING

3 perature of bloom treatment and tem-

perature of ozone exposure.
Figure 3 shows digital microscope im-
ages for the vulcanized IR as a model, in
which amount of wax was 0.0, 0.5, 1.0,
2.0 and 4.0 phr, respectively. The ozone
exposure tests of the vulcanized IR were
performed at -30°C and 40°C, respec-
tively, after bloom treatments at 23°C
and 40°C. The ozone cracks were depend-
ent upon the amount of wax, the tem-
perature for bloom treatment and the
temperature for ozone exposure. In most
cases, the ozone resistivity is high, when
the amount of wax increases; that is, the
larger the amount of wax, the smaller
the number of ozone cracks. In contrast,
the ozone cracks for vulcanized IR with
0.5 phr wax and vulcanized IR with 1.0
phr wax did not appear at -30°C after
bloom treatment at 40°C, whereas they
appeared for vulcanized IR with 2.0 phr
wax and vulcanized IR with 4.0 phr wax.
We considered that the temperature of
bloom treatment was a key factor for the
ozone degradation of the rubber.
Figure 4 shows a plot of amount of
Fig. 3: Digital microscope images for the vulcanized IR exposed with 50 pphm ozone after
bloomed wax versus temperature of
bloom treatment (20 magnifications).
bloom treatment for the vulcanized IR
mixed with 0.0, 0.5, 1.0, 2.0 and 4.0 phr
4 Fig. 4: The amount of wax, which was measured by gravimetric
bloomed wax for the method. The amount of bloomed wax
vulcanized IR measu- was large at 40°C, whereas it was small at
red by gravimetric me- 23°C. In addition, the amount of bloomed
thod in conjunction wax increased as the amount of wax in-
with digital micro-
creased. At -30°C after bloom treatment
scope images for the
at 40°C, the ozone cracks were found for
vulcanized IR exposed
with 50 pphm ozone the vulcanized IR with 2.0 and 4.0 phr wax
at -30°C after bloom in spite of the thicker wax layer. The ozone
treatment at 40°C cracks were not found for the vulcanized
(20 magnifications). IR with 0.5 and 1.0 phr wax, which pos-
sessed thinner wax layer.
SEM images for cross section of the
vulcanized IR with 0.0 and 2.0 phr wax
after bloom treatment are shown in Fig-
ure 5. In the SEM images, bloomed wax
was significantly distinguished from sur-
face and bulk of the rubber. As for the
vulcanized IR with 0.0 phr wax, no wax
5 appeared on the surface of the rubber. In
contrast, for the vulcanized IR with 2.0
phr wax, the bloomed wax appeared at
23°C. The thickness of the bloomed wax
increased as the temperature of bloom
treatment raised. It was, thus, assured
that the amount of bloomed wax in-
creased as the temperature of bloom
treatment raised.
Figure 6 shows surface morphology
for the vulcanized IR with 0.0, 0.5 and 4.0
Fig. 5: SEM images for cross section of the vulcanized IR with 0.0 and 2.0 phr wax after
phr wax, observed by SEM with a magni-
bloom treatment.
fication of 500, where pictures on the left

34 KGK · 03 2018 www.kgk-rubberpoint.de

 PRÜFEN UND MESSEN
TESTING AND MEASURING

side represent the vulcanized IR with 6

wax heated at 40°C after bloom treat-
ment at 40°C and pictures on the right
side represent those cooled at -30°C after
bloom treatment at 40°C. Both heating
and cooling after bloom treatment were
carried out in the presence of air. The
surface morphology for the vulcanized IR
with 0.0 and 0.5 phr wax was not de-
pendent on the temperature; that is, the
surface morphology at 40°C was similar
to that at -30°C. Especially, the smooth
wax layer of the vulcanized IR with 0.5
phr wax was maintained on the rubber
surface at -30°C. In contrast, the surface
morphology for the vulcanized IR with
4.0 phr wax was significantly dependent
upon the temperature. The surface was
smooth at 40°C, whereas it was rough at
-30°C. Some flaws appeared at -30°C.
Magnified image of the vulcanized IR
with 4.0 phr wax cooled at -30°C after
bloom treatment at 40°C is shown in
Figure 7. Rough wrinkles and flaws were
found in the wax layer. From the results,
it is hypothesized that the wax layer is
broken by heat shock. In an ordinary cir-
Fig. 6: The surface morphology for the vulcanized IR with 0.0, 0.5 and 4.0 phr wax, obser-
cumstance, the heat shock took place
ved by SEM (500 magnifications).
due to the difference in thermal contrac-
tion coefficient between rubber and
wax. Therefore, the thermal contraction 7 Fig. 7: The magnified
coefficients were measured for IR and SEM image of the vul-
wax, respectively. canized IR with 4.0 phr
Figure 8 shows temperature depend- wax cooled at -30°C
ency of thermal contraction coefficients after bloom treatment
at 40°C (1500 magnifi-
of IR and wax measured by TMA. The
cations).
thermal contraction coefficient of IR was
quite similar to that of the wax above
8°C. However, the thermal contraction
coefficient of IR was distinguished from
that of the wax below 8°C. The deference
was significant at -30°C; that is, the ther-
mal contraction coefficient of IR was
higher than that of the wax. The differ-
ence in the thermal contraction coeffi-
cients may result in a strain at an inter- due to the difference in the temperature wax layer. In the case of thin wax layer,
face between IR and wax. The strain may dependency of the thermal contraction the wax layer may flexibly deform with
be so large at -30°C that wrinkles and coefficients of IR and wax. The thermal the rubber substrate. Therefore, the wax
flaws generate. Therefore, the ozone ex- contraction coefficient of IR was distin- layer may effectively protect the rubber
posure test of the vulcanized IR with 4.0 guished from that of wax at -15 and 0°C, against ozone, since the wax layer com-
phr wax was carried out at four tempera- whereas it was similar to that of wax at 10 pletely covers the rubber due to the ab-
tures, i.e., -15, 0, 10 and 23°C. and 23°C. The different thermal contrac- sence of the flaw of the wax layer. In
Digital microscope images for the vul- tion coefficient at low temperature may contrast, in the case of thick wax layer,
canized IR with 4.0 phr wax are shown in cause the flaws of the wax layer, which the wax layer may not deform with the
Figure 9, in which the temperatures for results in ozone cracks of the vulcanized rubber substrate. The flaws of the wax
the ozone exposure test after bloom treat- IR. This suggests that the wax layer on the layer generate, since the strain energy of
ment at 40°C are -15, 0, 10 and 23°C. The surface of the vulcanized IR is broken to the wax layer is so significant due to the
ozone cracks were found for the vulcan- release the strain energy stored at inter- difference in the thermal contraction co-
ized IR with 4.0 phr wax at -15 and 0°C. In face between the rubber and the wax. efficient between rubber and wax.
contrast, the ozone crack was not found Based on our results, we may classify Therefore, ozone may penetrate through
for the vulcanized IR with 4.0 phr wax at the ozone degradation of rubber at -30°C the wax layer to the rubber due to the
10 and 23°C. This may be explained to be into two: that is, thin wax layer and thick flaws of the wax layer.

www.kgk-rubberpoint.de KGK · 03 2018 35

 PRÜFEN UND MESSEN
TESTING AND MEASURING

8 Fig. 8: Temperature References

dependency of
thermal contraction
coefficient of
vulcanized IR and wax
measured by TMA.
9
Fig. 9: Digital microscope images for the vulcanized IR with 4.0 phr wax, exposed with
50 pphm ozone at -15, 0, 10 and 23°C after bloom treatment at 40°C (20 magnifications).
Conclusions to the wrinkles and flaws of thick wax
Vulcanized IR with a paraffin wax as an layer. This was explained to be due to the
antiozonant was prepared to investigate difference in the thermal contraction co-
the effect of wax on the ozone degrada- efficient between IR and wax at -30°C.
tion of the vulcanized rubber at 40°C and From the results, it was found that the
-30°C, after bloom treatment at 40°C. At thick wax layer, which formed the wrin-
-30°C, ozone cracks appeared for the vul- kles and flaw, resulted in the ozone
canized IR with thick wax layer on the cracks of the rubber at low temperature,
rubber, while they did not appear for the even though it has a high ability to pre-
vulcanized IR with thin wax layer. The ap- vent the ozone degradation at high tem-
pearance of the ozone cracks was related perature.
[1] G. Y. Li, J. L. Koenig, Rubber Chem. Technol. 78
(2005) 355.
[2] S. L. Agrawal, S. Mandot, S. Bandyopadhyay,
R. Mukhopadhyay, A. S. Deuri, Prog. Rubber
Plast. Re. 21 (2005) 139.
[3] L. Pysklo, T. Glijer, T. Parys, Kautsch. Gummi
Kunstst, 51 (1998) 797.
[4] F . Cataldo, Polym. Degrad. Stabil. 72 (2001) 287
[5] NOC Gijutsu Note No.227: Nippon Gomu
Kyokaishi, 52 (1979) 724.
[6] S. Otomo, Nippon Gomu Kyokaishi, 87 (2014)
284.
[7] S. Ando, S. Fukamachi, Nippon Gomu Kyokai-
shi, 82 (2009) 45.
[8] R. W. Layer, R. P. Lattimer, Rubber Chem. Tech-
nol. 63 (1990) 426.
[9] F. Jowett, Elastomerics 111 (1979) 48.
[10] S. L. Agrawal, S. Mandot, S. Bandyopadhyay,
R. Mukhopadhyay, A.S.Deuri, Prog. Rubber
Plast. Re. 21 (2005) 139.
[11] F. Ignatz-Hoover, B. H. To, R. N. Datta, A. J. De
Hoog, N. M. Huntink, A. G. Talma, Rubber
Chem. Technol. 76 (2003) 747.
[12] P. J. Dimauro, H. L. Paris, M. A. Fath, Rubber
Chem. Technol. 52 (1979) 973.
[13] H. Sugimoto, M. Mizoe, Y. Yamamoto, M.
Ikenaga. Journal of Japan Society of Civil
Engineers 693 (2001) 73.
[14] Y. Takano, Nippon Gomu Kyokaishi 40
(1967) 248.
[15] M. Braden, A. N. Gent, Rubber Chem. Tech-
nol. 35 (1962) 200.
[16] A. Hartmann, F. Glander, Rubber Chem.
Technol. 29 (1956) 166.
[17] M. R. Ambler, J Polym. Sci. Part A-1 11
(1973) 191.
[18] R. Torregrosa-Coque, S. Álvarez-García, J. M.
Martín-Martínez, Int. J Adhes. Adhes. 31
(2011) 20.
[19] N. Urabe, F. Sakaguchi, Polymer friends for
rubber, plastic and fiber, 3 (1966) 184.

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