Polymer Degradation and Stability 186 (2021) 109514

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Polymer Degradation and Stability

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

Study on the ozone aging mechanism of Natural Rubber

Tingting Zheng a,b, Xiaoqian Zheng a,c, Shengqi Zhan a,c, Jing Zhou a,c, Shuangquan Liao a,c,∗
a
Key Laboratory of Advanced Materials of Tropical Island Resources (Hainan University), Ministry of Education.Haikou, 570228, P. R. China
b
School of Life and Pharmaceutical Sciences, Hainan University, Haikou, 570228, China
c
School of Materials Science and Engineering, Hainan University, Haikou, 570228, China

a r t i c l e i n f o a b s t r a c t

Article history: Regarded as a strategically crucial material, natural rubber (NR) plays an essential role in our daily life.
Received 15 November 2020 However, the corresponding rubber products have been facing the problem of aging in which the ozone
Revised 28 January 2021
aging of natural rubber accounts for a crucial position. Based on the concern, the related mechanism of
Accepted 3 February 2021
ozone aging for natural rubber was systematically studied in this work. Besides, to deeply understand
Available online 7 February 2021
the mechanism of ozone aging, we selected squalene, a small molecular substance with similar structure
Keywords: to natural rubber, to simulate the ozone aging process and analyze the molecular structure changes of
natural rubber natural rubber. After comprehensive characterization, the obtained results showed that the natural rubber
ozone molecular network, during the aging process, was destroyed and three newly-discovered free radicals
structure were generated (•H, •O2 − and •C=C), finally resulting in the weakened mechanical properties. We believe
mechanical properties this work can provide a more insightful view toward the relevant research on the ozonolysis mechanism
and the relationship between structure and performance as well as new ideas for the design of high-
efficiency antioxidants for NR.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction
Natural rubber (NR), deemed to be a strategically significant
material, has received great attention in the military, [1,2] medi-
cal, [3,4] industrial, [5,6] and agricultural fields [7] for a long time
owing to its unique chemical and physical properties [8-11]. How-
ever, due to the existence of unstable double bonds [12] and allylic
hydrogen, the properties of NR can be greatly affected when ex-
posed to light [13] heat, [14] oxygen, [15,16] ozone, [17-22] etc. As
a consequence, countless rubber products are discarded due to the
aging every year, which has a serious impact on the economy and
environment. To figure out a related mechanism, herein, is rather
important for the rubber industry. Previous studies have illustrated
that the rubber can be also aged and scrapped even if there is
a few pphm (parts per billion) of ozone in the air. Criegee et al.
[23-27] obtained the basic mechanism about the reaction between
ozone and double bonds after conducting a series of research about
olefins ozonide. When it comes to NR, Rugg, J. S., [28] Braden, M.
[29-31] and Buckley, D. J. [32] et al. studied the growth of cracks
for NR in an ozone environment, suggesting that the formation and
growth of cracks were linearly correlated with strain, ozone con-
centration and time. Further evidence was also demonstrated in
∗
Correspondence author: Shuangquan Liao
E-mail address: lsqhnu@hainanu.edu.cn (S. Liao).
Anachkov, M. P. et al’s work [33], They pointed out that the ratios
for ozonide, ketone and aldehyde of E-IR and Z-IR were 40:37:23
and 42:39:19, respectively, in the ozonolysis of 1,4-cis-polyisoprene
and 1,4-trans-polyisoprene solutions aged by ozone. Additionally,
according to the results of GPC and FTIR spectroscopy, Nor H.M.
et al. [34] found the relevant ozonolysis behavior of natural rubber
in chloroform solution, demonstrating that the relative intensity
of ozonides peaks such as carbonyl, ozonide, hydroxyl and/or hy-
droperoxide, in addition to the reduced average molecular weight
(<900) of NR, were enhanced while that for principal peaks of NR
(-CH2 -, -CH3 and C=C) were correspondingly weakened.
Although the ozonolysis process has been thoroughly studied,
many research results, to the best of our knowledge, have lain
on the study of the ozonolysis for alkenes. Up to now, there are
few authoritative representations and discussions on the current
state of affairs in terms of the ozonolysis. Besides, it should be
noted that systematic studies of the mechanism and the proper-
ties for cured neat NR aged by ozone are missing. Therefore, to
clarify the ozone aging mechanism of NR, a reliable theoretical ba-
sis for the anti-aging research of natural rubber is rather neces-
sary. In this work, the domestic SCR-WF was selected as the re-
search object, and ozone aging was performed on NR I-dumbbell
rubber specimen in Ozone Aging Chamber at room temperature for
a different time and ozone concentrations. The evolutions of struc-
ture and properties were investigated to assess the aging mecha-
nism and analyze the following consequences. We believe that this

https://doi.org/10.1016/j.polymdegradstab.2021.109514
0141-3910/© 2021 Elsevier Ltd. All rights reserved.
T. Zheng, X. Zheng, S. Zhan et al.
Table 1
Basic physical and chemical properties of NR.
impurity [%] Ash[%] Volatile matter[%]
0.01 0.28 0.40
work can provide a proof-of-principle concept for understanding
the mechanisms of ozone aging and new ideas for the design of
high-efficiency antioxidants for cured neat NR.
2. Experimental Section
2.1. Materials
NR was provided by Hainan Rubber Industry Group
Co., Ltd. (China). Zinc oxide, sulfur, stearic acid, and 2-
Mercaptobenzothiazole were obtained from Shanghai Yuanye
Biotechnology Co., Ltd.;
2.2. Preparation of Cured NR Samples
The curing agents were successfully mixed with NR in an
open twin-roll mill at room temperature with a friction ratio of
1:1.2. The curing formula for NR was designed as following: NR
100 phr, sulfur 3.5 phr, ZnO 6 phr, stearic acid 0.5 phr, and 2-
Mercaptobenzothiazole 0.5 phr. After mixing, the compounds were
compressed at 145°C, and the optimum curing time was deter-
mined by a vulcameter.
2.3. Ozone aging NR
The I-dumbbell-shaped sample was obtained by cutting shear
according to GB/T528, the ozone aging was performed on a UA
2074 Ozone Aging Chamber. According to GB/T 7762, the sample
was pre-stretched to 20% strain for 48 hours in dark before ozone
aging. The ozone concentrations were 50pphm and 100pphm, re-
spectively,(room temperature and < 10% humidity) and the aging
time varied from 1 to 9 hours.
2.4. Characterizations
Fourier transform infrared spectroscopy (FTIR) was performed
on a Bruker Tensor 27 spectrometer.
Crosslinking density was determined by the equilibrium
swelling method in toluene and calculated according to the clas-
sical Flory-Rehner equation [35]:
 1
 WF according to GB/T 8081 (Rubber, raw natural-Guidelines for
−ln(1 − ϕr ) − ϕr − χr ϕr 2 = nV0 ϕr 1/3 − ϕr
2 that there was no extra impurity existing in NR during the pro-
ρ index of NR were 36 and 77.6, respectively, indicating that the NR
Mc =
n was easy to be processed. The plasticity retention index (PRI), valu-
where ϕ r is the polymer volume fraction in the swollen net-
work, V0 is the molar volume of the solvent (106.2 mL mol−1
for toluene), χ r is the Flor-y–Huggins polymer–solvent interaction
term (0.393 for NR/toluene), n is the average number of movable
chain segments per unit volume (mol mL−1 ), Mc is the average
mass of network chains, and ρ is the density of NR (0.913 g mL−1
for NR).
In detail, samples were soaked in toluene at 25 °C for 7
days, and the solvent was then rapidly removed from the swollen
sample surface by filter paper. The samples were subsequently
weighed and dried in a vacuum oven at 80 °C to reach the con-
stant weight.
X-ray photoelectron spectroscopy (XPS) was conducted on a
Thermo ScientificTM K-AlphaTM+ spectrometer equipped with a
Polymer Degradation and Stability 186 (2021) 109514
nitrogen content [%] P0 PRI[%] Mooney Viscosity
0.44 36 96 77.6
monochromatic Al Kα X-ray source (1486.6 eV) operating at 100W.
Samples were analysed under vacuum (P < 10−8 mbar) with a pass
energy of 150eV (survey scans) or 25eV (high-resolution scans). All
peaks were calibrated with C1s peak binding energy at 284.8eV
for adventitious carbon. The experimental peaks were fitted with
XPS-Peak software to evaluate the variation of the O/C atomic ra-
tio during the ozone aging.
The mechanical property was performed on dumbbell-shaped
samples (115mm × 6mm × 2mm and a gauge length of 25mm)
by a Gotech AI-30 0 0 instrument at room temperature. For uniaxial
tensile tests, the extension rate was at 500mm min−1 . The tensile
strength retention rate was calculated by the following Equation:
 
Tensile strength retention rate (% ) = σaged /σunaged × 100% (3)
where σ aged and σ unaged are the tensile strength of the aged and
unaged specimens, respectively.
2.5. Squalene simulating ozone aging of NR
20ml of squalene was put into a round-bottom flask and then
stirred at an ozone inlet flow of 15g h−1 . 0.5ml sample was taken
out every two minutes. Fourier transform infrared spectroscopy
(FTIR) was performed on a Bruker Tensor 27 spectrometer.
The electron paramagnetic resonance (EPR) spectrum was mea-
sured by a Bruker A300 EPR spectrometer (298 K, 9.852 GHz) at
ambient temperature. 10 mg min−1 of O3 was poured into 10ml of
squalene. After stirring for 5 minutes, 200μl of sample was taken
out for testing. Before testing, 200μl of 100 mM spin trapping
agent 5,5-Dimethyl-1-pyrroline N-oxide (DMPO) was added to the
sample, and the solvent of DMPO was water.
3. Results and discussion
3.1. Analysis of physical and chemical properties of NR
The basic physical and chemical properties of NR, shown in
Table 1, were firstly investigated, where the related impurity, ash,
volatile matter, and nitrogen content were 0.01%, 0.28%, 0.40%, and
0.44%, respectively. These data were up to the standard of SCR
(1) the specification of technically specified rubber (TSR)), indicating
duction process. The initial plasticity (P0 ) and plasticity retention
(2)
ing at 96%, also illustrated that NR had good oxidation resistance.
3.2. The change of the surface of NR during ozone aging
As shown in Fig. 1, the surface of initial NR was smooth while
some mild cracks occurred on the NR surface after one hour treat-
ment of ozone and the direction of cracks was perpendicular to
the external force [36,37]. As time went by, the cracks became
more noticeable and deeper. Moreover, the cracks firstly occurred
in the center of the NR surface and extended continuously to the
surroundings. However, there was no crack in the interior of the
sample, revealing that ozone aging processes were initiated at the
surface of NR. These obtained results demonstrated that the NR’s
ozone aging process was a continuous damaging process from the
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T. Zheng, X. Zheng, S. Zhan et al. Polymer Degradation and Stability 186 (2021) 109514

Fig. 1. Surface morphology changes of NR (pre-stretch 20%) by different Ozone (50pphm) aging time.

tity of cracks presented an undulate changed trend (up-down-up).

We assumed that when ozone attacked NR, the cracks appeared
on the surface of NR firstly, then extended in the NR along with
the force direction and accompanied by the increasing amount of
cracks, which was well matched with the results in Fig. 1. Mean-
while, the size of the cracks also increased continuously. The ad-
jacent cracks were combined to form the new cracks, resulting in
the increased mean size and the decreased number of cracks.

3.3. The change of molecular structure of NR during ozone aging

The influence of ozone aging on the molecular structure for NR

was further evaluated by FTIR. Fig. 3 showed the FTIR spectra of NR
before and after ozone aging at the different ozone concentrations.
Fig. 2. The trade of NR surface crack’s size during different ozone (50pphm) aging
Fig. 3a and c-0h showed the FTIR spectrum of NR before aging in
time. which the peaks at 2958, 2848 and ~1660 cm−1 were contributed
to the asymmetrical stretching vibration of -CH3 , -CH2 , and C=C
Table 2 respectively [38]. After ozone aging, the absorption strength of
Crack rating of NR vulcanizate with different ozone (50pphm) aging time. C=C bond was weakened, indicating that the C=C of NR was par-
Aging time [h] 0 1 2 3 4 5 6 7 8 9 tially destroyed during the ozone aging process. It is worth not-
ing that the consumption of primary ozonide was also observed
Crack grade 0 1b 2c 2c 2c 2c 2c 2c 2c 2c
since the peak at 1260 cm−1 (C–O–C deformation of epoxide ring)
can be referred to [39]. As shown in Fig. 3b and d, the density of
characteristic peak for C=O stretch of lactones [40] appearing at
middle parts to the sides, and the surface to the interior. Addition- ~1737cm−1 was enhanced in NR by extending ozone aging time,
ally, the concentration of ozone also played an important role in which was similar to the reported work [41] (aging can disrupt
aging process in which the time to generate crack at an ozone con- the vinyl groups and result in the generation of the carbonyl group
centration of 100pphm was at least 0.5h, which was less than that in the rubber). It is worth mentioning that there was a new peak
for 50pphm (1h), demonstrating that the ozone concentration had at ~1600cm−1 emerging on NR after ozone aging, indicating the
a certain effect on the ozone aging of natural rubber. It is worth presence of the typical characteristic peak of C=C-C=C [42]. Since
mentioning that the color of the NR surface hasn’t been changed the compounds with a conjugated double bond on their structures
too much. are more prone to addition, polymerization, and Diels-Alder diene
To confirm the change of crack on surface for NR, the auxiliary synthesis reactions, natural rubber can be protected against ozone
software nano-measure was used to measure the size of the crack aging according to these intrinsic characteristics [43].
according to GB/T 11206 (Standard test method for rubber deterio-
ration - Surface cracking), shown in Fig. 2 and Table 2. The result 3.4. Crosslink density change of natural rubber during ozone aging
showed that the size of crack continuously increased with ozone
aging time. As the aging time increased (Fig. 2), three stages can Crosslink density, which is highly relevant to mechanical prop-
be found where the changes for mean width, length, and quan- erties, was subsequently studied to investigate the interaction of

3
T. Zheng, X. Zheng, S. Zhan et al. Polymer Degradation and Stability 186 (2021) 109514

Fig. 3. FTIR spectra of NR with different ozone aging time at the different ozone concentrates.

Fig. 4. Crosslink density and Mc of NR before and after ozone aging at different ozone concentrations (a) 50pphm, (b) 100pphm.

the molecule chain. The cured NR will form a 3D-crosslink net- Table 3
O/C ratio of NR before and after aging obtain
work among rubber molecule chain, and the degree of crosslinking
from fig. 5.
can be expressed by the crosslink density or the average molec-
ular weight between the crosslinking points. As shown in Fig. 4, Aging time [h] 0 3 6
the crosslink densities of NR were 1.02 × 10−4 mol mL−1 and O/C ratio [%] 28.0 33.5 35.8
0.97 × 10−4 mol mL−1 before and after ozone aging (50pphm for O/C increase [%] 19.6 27.8
6h), respectively, which displayed ~4.9% difference, indicating that
the crosslinked network was degraded after ozone aging. Moreover,
due to the breakage of chemical bonds, a looser inter-molecular 3.5. Analysis of ozone aging degree of NR
alignment was generated, meaning the average relative molecular
weight between two adjacent cross-linking points, to a certain de- Oxidation can increase the oxygen/carton (O/C) atomic ratio of
gree, increased. As the aging time went by, the crosslink density the samples [45]. Therefore, XPS was then applied to study the
of NR was not maintained at a stable level, and the overall trend, change in the O/C ratio for NR before and after the ozone oxida-
however, showed a declining trend. This result is similar to the tion. The fitted peaks are shown in Fig. 5b-g, the O1s peak region
change of crack sizes for NR. During the process, the slightly in- of the NR had two-component peaks: C=O/O–C=O (532.0eV) and
creased crosslinking density may be caused by the crosslinking of C−O−C (533.5eV). Besides, the C1s peak region of the NR had three
some molecular chains. According to Choi’s work, [44] the incre- component peaks: C=C (284.8eV), C−O=C (285.9eV) and C−O−C
ment of crosslink density generally resulted from the existence of (288.6eV), proving that the double bond of natural rubber was de-
free sulfur content, which can lead to the post-curing process dur- stroyed to form C-O and C=O bonds after ozone aging, which is
ing the aging period. These phenomena indicated that natural rub- well consistent with the FTIR results.
ber was in a state of chain scission and cross-linking during ozone Moreover, the relative ratios for O/C of each samples were then
aging, and its cross-linking density ultimately tended to decrease. calculated by dividing the total O1s and C1s peak areas. As shown
Therefore, the chain-breaking tended to dominate this process. in Fig. 5 and Table 3, the O/C ratio near the surface was 28.0 to 100

4
T. Zheng, X. Zheng, S. Zhan et al.
Fig. 5. XPS survey spectra of NR before and after ozone aging.
for the NR before ozone aging, demonstrating that some extent of
oxidation to the surfaces of the samples had occurred at 145 °C in
the mold [45]. Thereafter, the O/C ratio was changed to 33.4/100
after Ozone aging for 3 hours, which was 19.6% higher than that
of NR before ozone aging. Additionally, as the aging time accumu-
lated, the O/C ratio increased steadily in NR surfaces, revealing that
the aging degree of ozone in NR had been enhanced with the time.
3.6. Squalene simulating ozone aging of NR
To have a deeper understanding of the mechanism of ozone ag-
ing, we selected squalene, a small molecular substance similar in
structure to natural rubber, to simulate the ozone aging process
of natural rubber, and analyzed the molecular structure changes of
natural rubber.
As expected, the typical characteristic peak C=C at ~1660cm−1
for squalene gradually disappeared with the increase of aging time
(Fig. 6a and 6b). Besides, five new peaks appeared at ~1730cm−1 ,
~1717cm−1 , ~1522cm−1 , ~1244cm−1 , and ~1071cm−1 , respectively,
indicating that the double bonds in squalene were destroyed by
ozone along with the generation of C=O and C-O-C. Among these,
The peaks at ~1522cm−1 , ~1730 cm−1 and ~1717cm−1 represented
an enol tautomer of a beta-diketone [40], C=O bond of alkyl alde-
hydes [39] and ketones [40], respectively, indicating that the squa-
lene was converted to enol tautomer of a beta-diketone, alkyl alde-
hydes and ketones after ozone aging, which is similar to the re-
ported results in Criegee’s [27] N.S. Allen [40] and F. Cataldo’s
works [21,36,37,46]. The broad ranges of bands from 1280 to 1150
and 1114 to 1050 cm−1 were associated with a mixture of aliphatic
esters and ethers. The latter was more specifical to be the peaks of
–C–O–C– in ester [40]. Furthermore, the reaction between squalene
and O3 was confirmed by ESR analysis (Fig. 6c, d), where DMPO
(50 mM) worked as the spin trapping agent. It can be seen from
Fig. 6c that no free radical signal was observed in the spectrum of
squalene (Fig. 6c-blue spectrum) before the reaction with ozone.
5
Polymer Degradation and Stability 186 (2021) 109514
After 5 min introduction of ozone, the signal peak of free radi-
cals can be clearly observed. After peak fitting (Fig. 6c-olive green
spectrum) (Fig. 6d), three kinds of free radicals can be clearly ob-
served, including hydrogen radical (DMPO-•H with nine lines) [47],
superoxide radical (DMPO•O2 − , with an intensity ratio of 1:1:1:1)
[48] and olefin radical (DMPO-•C=C) [49]. This new discovery can
provide an important basis for the future research on the anti-
ozone aging of natural rubber.
Therefore, we come up with a potential aging process, which is
shown in Scheme 1. The black arrows were received from prede-
cessors’ research, [27,36,37,46,50] the red arrow was three newly-
discovered free radicals in this work.
According to the above analysis, we hypothesized the possible
mechanisms for the ozone aging of NR as follows:
(I) The ozone aging of NR is a process from the surface to the
inside and from the middle to the two sides.
(II) The ozone aging process of natural rubber is accompanied
by the damage of inherent crosslinking and chain structures,
and the ozone molecule works as a ’scissors’ to cut the
molecular chain of natural rubber and induces the gener-
ation of cracks on the rubber surface perpendicular to the
stretching direction.
(III) Ozone aging can disrupt the vinyl groups and lead to the
generation of C=O compounds (alkyl aldehydes and ke-
tones), aliphatic esters and ethers in NR. Besides, free radi-
cals such as •H, •O2 − and •C=C radicals are generated, which
may accelerate the aging of NR.
3.7. Mechanical properties
The mechanical properties of NR with different ozone aging
times were further investigated. And, the trend of tensile testing
results in Fig. 7a and c showed the typical stress-strain curve of
vulcanized NR. Before ozone aging, the tensile strength and elon-
gation at break were ~20.89 MPa and ~748.2%, respectively, while
T. Zheng, X. Zheng, S. Zhan et al. Polymer Degradation and Stability 186 (2021) 109514

Fig. 6. FTIR (a and b) and EPR (c and d) spectra of squalene before and after reacting with ozone (DMPO worked as the spin trapping agent).

Scheme 1. Schematic diagram of the potential mechanism for NR ozone aging.

these for the samples continuously decreased to ~11.43 MPa and
~699%, respectively, after ozone aging at 50 pphm for 5h. The ten-
sile strength for 5h aging time was ~45.28% lower than that of the
raw NR. Meanwhile, it was obvious that tensile strength, elonga-
tion at break and strength at ~300% of NR were decreased with
aging time, indicating that ozone aging can greatly affect the me-
chanical properties of natural rubber, which was even worse than
that of thermo-oxidative aging [51] and ultraviolet aging [52]. The
reason was that the cracks appeared on the surface of the sam-
ple, leading to the serious damage for NR when NR contacted
with ozone. However, when NR was exposed to the conditions
of thermo-oxidative and ultraviolet, no cracks appeared, demon-
strating that the impact caused by thermo-oxidative and ultravi-
olet were not as serious as that for ozone. Additionally, it was

6
T. Zheng, X. Zheng, S. Zhan et al.
Fig. 7. Mechanical properties (a) 50pphm (b)100pphm (c) (d) elongation at break, tensile strength, 300% strength and tensile strength retention rate of NR at different ozone
aging time.
found that the tensile strength and elongation at break of NR at
50 pphm were slightly higher than these of NR at 100 pphm at the
same aging time, suggesting that the concentration of ozone also
influenced NR although the influence was slighter. Furthermore,
the tensile strength retention rate of all ozone aging NR decreased
with aging time, as shown in Fig. 7d, which further demonstrated
that the mechanical properties can be decreased with aging time.
4. Conclusion
In this study, the properties of ozone aging NR were studied.
It is worth noting that ozone aging time plays a very important
role in the process of ozone aging, and the effect of ozone is based
on the concentration. The results show that the surface morphol-
ogy, molecular structure and mechanical properties of NR by ozone
aging have been changed dramatically. The ozone aging of natural
rubber is a process from the surface to the inside and from the
middle to the two sides. During this period, the size of the cracks
increased with aging time. With the extension of aging time, the
physical properties of natural rubber such as tensile strength and
elongation at break were correspondingly reduced since the NR
molecular chain network structures and cross-linking points were
both destroyed. The simulated aging process of NR by the squa-
lene proved that ozone can destroy C=C in the molecular chain
of olefins and form alkyl aldehydes, ketones, aliphatic esters and
ethers. Besides, it will generate superoxide, olefin and hydrogen
radicals.
Declaration of Competing Interest
The authors declare no competing financial interests or personal
relationships that could have appeared to influence the work re-
ported in this paper.
Acknowledgments
This work was supported by Chinese Academy of Sciences [No.
XDC06010100], Hainan Provincial Department of Science and Tech-
nology [No. ZDKJ2016020], Guangdong Science and Technology De-
7
Polymer Degradation and Stability 186 (2021) 109514
partment [2020B020217003], and Education Department of Hainan
Province [Hyb2019-11].
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