Sulfur vs.

Peroxide Crosslinking ®

of Therban HNBR Elastomers

Based on Lit. # FK-0447e
Technical Information Bulletin 01.99
Page 1 of 20

tib
Abstract
Sulfur and peroxide are commonly used crosslinking agents with general purpose elastomers. A brief
history of sulfur and peroxide crosslinking is given. Guidelines to reduce cure time and improve aging
resistance for both sulfur and peroxide crosslinking are outlined. Vulcanizate properties of hydrogenated
nitrile rubber (HNBR) compounds crosslinked with sulfur and peroxide (in the presence of various
coagents) are examined.

Introduction
An amorphous polymer gains dimensional stability with crosslinking. The formed crosslinks prevent the
polymer from flowing under shear. The process of crosslinking is called vulcanization, and the chemicals
used for crosslinking are called curing agents or cure system. A crosslinked rubber (vulcanizate) shows
the following differences when compared with an uncrosslinked rubber:

• the vulcanizate undergoes deformation upon Common Cure Systems

stretching and when released can recover Cure System Polymers
almost completely its original dimension
Sulfur NR
over time IR
SBR
• the vulcanizate does not dissolve in a good BR
solvent for uncrosslinked rubber but shows EPDM
swelling IIR
NBR
• the properties of a vulcanizate are less HNBR
sensitive to temperature. Peroxide CPE
CSM
Several cure systems are used in the rubber MQ
industry, and each cure system has its own HNBR
EVM
merits. Selection of a cure system is based upon FKM
several considerations such as functional TFE/P
performance desired of the vulcanizate or article Metal Oxide CSM
and processing and safety risks of the curing CR

process. Amine ACM

EAM
FKM
Table 1 gives five common cure systems for ECO
various classes of rubbers. The cure systems,
Phenolic Resin IIR
which do not use free sulfur, are also known as
sulfurless cure systems. Table 1 Common Cure Systems

Paper presented at a meeting of the

Rubber Division, American Chemical
Society, Indianapolis, Indiana,
May 5-8, 1998.
 Sulfur vs. Peroxide Crosslinking
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The purpose of the present review is to compare sulfur and peroxide cure systems. Therban® is used in this review
because, depending on the residual double bond content, it can be crosslinked by either sulfur or peroxide.

Technological History of Sulfur Vulcanization 1

A brief historical account of technological advancements History of Vulcanization
in sulfur vulcanization is shown in Table 2. From this Inorganic Accelerator
it can be seen that the basic concept of Goodyear’s
1839 Goodyear discovered vulcanization of NR
discovery of the use of sulfur for vulcanization still using sulfur and basic lead carbonate
endures after 160 years. (patented in 1844)
1843 Hancock demonstrated industrial use of
Vulcanization using sulfur alone is sluggish, but, sulfur vulcanization process
when the sulfur level is increased to make the Organic Accelerators
vulcanization faster, a problem of sulfur blooming 1906 Oenslager used aniline in sulfur
arises. Organic accelerators were developed to vulcanization process
overcome the sluggishness of sulfur vulcanization 1909 Thiocarbanilide replaces aniline
and to prevent blooming of unreacted sulfur. 1910 Bayer receives the first patent on organic
accelerators aryl guanidine and
In 1906 Oenslager used aniline to accelerate sulfur dithiocarbamate

vulcanization. However, aniline is poisonous and, 1920s ZnO and stearic acid used as activators.
Accelerators thiuram and thiazoles were
being liquid, was difficult to use. Thiocarbanilide, a introduced
safer solid derivative, replaced aniline to accelerate 1925 MBT, derivatives MBTS and ZMBT
sulfur vulcanization and reduce cure time from introduced
several hours to about one hour. In 1910 Bayer 1930s Aldehyde-amine and guanidine used in
received the first patent on organic accelerators based the tire industry
on guanidine and dithiocarbamate derivatives. Next, 1932 Discovery of sulfenamides (Bayer part of
I.G. Farben)
in the 1920s, it was shown that zinc oxide and stearic
1938 Bayer introduces commercial
acid in combination with organic accelerators were
sulfenamides
useful in activating the curing reactions. In 1925
1970 Discovery of retarders/inhibitors of
mercaptobenzothiazole (MBT), its disulfide (MBTS) vulcanization (CTP)
and zinc derivatives (ZMBT) were introduced. Relative 1990s Sulfenimides introduced
to guanidine derivatives MBT overcame the retarding To date No new major class of commercial
effects of acid channel blacks, provided a rapid rate of accelerators introduced
cure, exhibited resistance to reversion on overcure,
Table 2 Technological History of Vulcanization
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Page 3 of 20

and offered good aging resistance. However, MBT and its derivatives were scorchy compared to guanidine
derivatives. It became apparent that a blocked thiol hydrogen MBT derivative was needed. Hence, the sulfenamides
were developed. Once again, in 1938, Bayer was the first to introduce commercial sulfenamides. The sulfenamide
derivatives soon became popular because, depending upon the amine used, a spectrum of curing speed from
fastest (CBS) to slowest (DCBS) was available. About 40 years after the introduction of sulfenamide, retarders to
improve the processing safety without sacrificing cure speed were introduced. No new major class of commercial
sulfur accelerators has since been introduced.

A comparison of relative scorch against relative cure time for various classes of accelerators on equimolar/
equivalent weight basis with 2 parts (phr) sulfur for typical NR tread compound is shown in Figure 1.2 The basis of
normalization is the rheometer cure characteristics of CBS equal to 100 percent; scorch ts1 and cure time t 90.
It should be noted that:
• sulfenamides are least scorchy giving delayed action yet relatively fast cure rate.
• scorchy accelerators are not necessarily fastest curing; for example, thiurams and dithiocarbamates are quite
scorchy and cure very rapidly. Thiazoles are fairly scorchy but cure comparatively slowly.

Comparison of Accelerators

200
Normalized t90 (base CBS = 100)

150
MBT
DCBS
DIBS
MBTS MBS
100 ZnDBC TBBS
CBS
TMTM
50 TMTD
ZnDMC

0
0 50 100 150 250

Normalized tS1 (Base CBS = 100)

Figure 1 Comparison of Accelerators (equimolar) in NR Tread Compound
Cure Time t90 @ 160 °C vs. Scorch Time @ 135 °C, Base CBS = 100
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Scheme of Rubber Vulcanization Using Sulfur and MBT Sulfenamide

The process of rubber vulcanization is schematically Scheme of Rubber Vulcanization
described in Figure 2. The mechanism of acceleration Rubber Compound Containing Activators ZnO and
varies with accelerator chemical class, activators used Stearic Acid + Sulfur + Accelerator(s)
and polymer considered. Therefore the precise low heat
mechanism of vulcanization using an accelerator is a
subject of controversy. The controversy stems from Active Sulfurating Agent
the complex nature of the reactions occurring medium heat
simultaneously during the vulcanization process.3, 4
Rubber Bound Intermediate, a crosslinker precursor
Krebs’s5 work based on reaction studies of sulfur with high heat
amines and sulfide ion suggested that, in addition to
homolytic thermal cleavage at high temperatures, the Crosslinked Rubber Network
sulfur S8 ring undergoes rapid ionic cleavage at lower Figure 2 Scheme of Rubber Vulcanization
temperatures in the presence of an amine or sulfide
ion. This active polysulfidic chain, shown in Figure 3,
then ties the rubber polymer chains thus giving rise Scheme of Acceleration
to sulfur crosslinks of varying ranks such as
monosulfide, disulfide, and polysulfide. This S8 S S6 S
mechanism satisfactorily explains sulfenamide R1
N
Typical MBT
accelerated vulcanization, because both amine and Sulfenamide
C S N
S R2
sulfide fragment generation is possible. This is due
to the low energy required to break a sulfur-nitrogen S8+NR3 R3 N S7 S-
S8+S= -S S S5 S S-
bond relative to carbon-sulfur and carbon-nitrogen.
Morrison and Porter4 give a classical discussion of Bond Energy (Kcal/mol) at 298 K (25 deg C)
C-N 167
the influence of crosslinks with varying sulfur ranks. C-N 184
S-N 111

Figure 3 Scheme of Acceleration Using MBT

Sulfenamide Accelerator
Sulfur vs. Peroxide Crosslinking
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Guidelines for Sulfur Crosslinking
Various approaches and their problems are outlined in Table 3. In sulfur cure, zinc oxide, or magnesium oxide,
stearic acid or other fatty acids or its metal salts are required to activate the curing reaction using accelerators,
depending on the objectives of the cure.
Guidelines for Sulfur Vulcanization
Objective
1. To reduce cure time
2. To improve aging resistance
3. Effect of (S/accelerator) ratio
on fatigue life
4. Curing temperature
5. Activators
Table 3 Guidelines for Sulfur Vulcanization
Approach
• Use a faster accelerator
• Increase accelerator level
• Increase accelerator level and
reduce S level (EV system)
• Use high (accelerator/S) ratio,
e.g., EV system
EV:
CBS 1.5 phr
DTDM (S-DONOR) 1.5
TMTD 1.5
S1 LINKS = 46%
(S2 + Sx) = 54%
• Conventional cure gives higher
polysulfidic links and better
fatigue resistance
• EV gives higher monosulfidic links
and poor fatigue resistance
• Tensile strength decreases as
Sx > S1 > C –– C
• As cure temperature increases, time
to reach optimum cure decreases
• ZnO or MgO is required to develop
full potential of accelerators
• Stearic acid or salts of fatty acids are required
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Problems
• Scorchiness increases (use retarder)
• Modulus increases hence elongation
and tear resistance decrease
• Scorchiness increases (use retarder)
• High proportion of monosulfidic links,
loss of dynamic flex fatigue properties
CONVENTIONAL CURE
S 2.5 phr
CBS 0.6
S1 = 0%
(S2 + Sx) = 100%
• Higher compression set and reversion
possible due to breakdown of Sx to S1
• Lower compression set and S1, can
crystallize hence higher brittleness
point temperature
• Higher temperature causes reversion
in conventional cure system, i.e. Sx
break down to S1
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To reduce cure time, use of a faster accelerator makes the process scorchy so that a retarder becomes necessary to
increase the processing time. If the accelerator level is increased, the modulus increases and a tighter cure with
lower tear strength is obtained. Thus there are trade-offs in the properties, which need to be optimized.

In comparison with peroxide-cured vulcanizates, sulfur-cured vulcanizates show, in general, poor aging resistance,
higher compression set and better dynamic properties. This is because the longer polysulfidic crosslinks eventually
reduce themselves into shorter disulfide links.

To improve aging resistance, a high accelerator to sulfur ratio referred to as efficient vulcanization (EV) system is
used. This system gives a higher proportion of monosulfidic crosslinks, which are less flexible than polysulfidic
and thus lower dynamic properties. The conventional cure system, high sulfur to accelerator ratio, gives a higher
proportion of polysulfidic crosslinks and hence better dynamic fatigue properties. However, due to a higher
proportion of polysulfidic crosslinks, the compression set is high.

Increasing the temperature to reduce cure time causes reversion in a conventional cure system. This is due to the
breakdown of polysulfidic to stable monosulfidic crosslinks.

Scheme of Rubber Vulcanization Using a Peroxide

The typical reaction6 occurring during vulcanization Scheme of Peroxide Vulcanization
using a peroxide (Figure 4) consists of three steps:
1. Homolytic breakdown
R–O–O–R ∆ 2RO •
1. homolytic breakdown of a peroxide into two
peroxide
alkoxy free radicals
2. Abstraction of hydrogen from polymer
2. abstraction of hydrogen from the polymer
P–H+R–O• P • + ROH
3. combination of two polymer radicals to form a polymer
carbon-carbon crosslink. 3. Combination
P•+P• P—P
The formation of the carbon-carbon bond is the
crosslinked polymer
reason for greater stability of a peroxide vulcanizate. It
Figure 4 Scheme of Peroxide Vulcanization
is important to select a peroxide with a suitable half-
life in order to obtain optimum cure, because half-life
is the time required for half of the peroxide curing
agent to decompose.
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Guidelines for Peroxide Crosslinking

Unlike sulfur cure, filler selection in a peroxide cure Common Cure Systems
is important, i.e., avoiding acidic filler to prevent 1. Use basic fillers and avoid acidic ones
cationic dissociation of a peroxide. Oil selection
2. Use paraffinic oils, avoid naphthenic and
should avoid naphthenic and aromatic oils as these aromatic oils
scavenge the free radicals required for crosslinking. 3. To increase scorch use radical scavengers,
This sometimes makes it necessary to select proper such as coagents
antioxidants. Depending on the cure temperature and 4. Use appropriate half-life peroxide
half-life of a peroxide, post curing may be necessary. 5. Post cure may be necessary
Table 4 describes these guidelines.
Table 4 Guidelines for Peroxide Cure

Degree of Crosslinking and Type of Crosslinks

It is well established that the degree of crosslinking strongly influences the following properties:

• physical properties such as tensile stress, elongation at break

• tear resistance
• dynamic damping and rebound resilience
• compression set
• resistance to swelling.
The type of crosslinks such as long polysulfidic (C–Sx–C, x > 3) or short carbon-carbon (C–C) and monosulfidic
(C-S-C) affect the properties of a vulcanizate.

Excellent tensile strength, rebound resilience, and flex fatigue properties are obtained with polysulfidic crosslinks,
while resistance to heat aging and compression set are best with shorter crosslinks.
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Effect of Crosslinking on Glass Transition Temperature

The crosslinking of a rubber polymer reduces the chain flexibility and raises its glass transition temperature (Tg).
The variation in Tg can be appreciated by noting that curing natural rubber (NR) with a high level of sulfur yields a
hard vulcanizate called ebonite.

Figure 57 shows an example of shear modulus of NR crosslinked using sulfur, radiation, and dicumyl peroxide
(DCP). It can be seen that as the level or concentration of crosslinking agent increases, the shear modulus
increases and a shift in glass transition temperature takes place. A large shift in Tg in the case of sulfur
vulcanization is due to an intramolecular cyclization involving sulfur that reduces the mobility of the polymer
backbone. A similar shift occurs for peroxide and radiation cured polymer at a higher level of crosslinking.

Glass Transition Temperature as a Function of Crosslink System

G' Sulfur Crosslinked Radiation Crosslinked DCP Crosslinked

(N/mm ) 22

103

102

101 Mrad
%S 30 335
170 %DCP 35
20
100 10
10 85 5
0 0 0
10–1
–100 –50 0 50 100 150 –100 –50 0 50 100 150 –100 –50 0 50 100 150 (°C)

Figure 5 Glass Transition Temperature as a Function of Crosslink System

NR Crosslinked with Sulfur, Radiation, and Dicumyl Peroxide (DCP)7

A relationship,6 temperature TgX = Tg + KX • ρ , for a sulfur crosslinked network has been proposed; where
TgX = glass transition temperature of network, Tg = glass transition of uncrosslinked NR, KX = a constant and ρ =
number of crosslinks per unit volume.

For a peroxide crosslinked polyisoprene (IR) network, TgX increases by about 6°C every 1020 crosslinks per gram.
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Effect of Sulfur and Peroxide Crosslink Systems in Therban®

The HNBR class of elastomers is produced by selective hydrogenation (Figure 6) of the double bonds of NBR.
Thus, the complete hydrogenation would lead to saturated products that can be crosslinked only with peroxides or
by high-energy radiation. The technical advantage of hydrogenation is increased heat aging resistance compared to
the base NBR.

Hydrogenation Chemistry

Nitrile Rubber (NBR)

—[–C–C=C–C–]—[–C–C–]—[–C–C–]—
X Y Z

C C N
C
+ Hytrogen, Catalyst

Hydrogenated Nitrile Rubber (HNBR)

—[–C–C=C–C–]—[–C–C–C–C]—[–C–C–]—[–C–C–]—
X-A A Y Z

CH2 C N
CH3
Figure 6 Hydrogenation Chemistry

Incomplete hydrogenation gives a partly unsaturated polymer that can be crosslinked with sulfur or peroxides. Sulfur
crosslinking is used when adhesion to fabric or metal reinforcement is required, while peroxide crosslinking is
used when excellent aging resistance is required. Such HNBR polymers are characterized by the content of residual
double bonds (RDB), expressed as a percentage calculated on the basis of the original double bond content of NBR.
 Sulfur vs. Peroxide Crosslinking
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Compounds Compared (Table 5)

Therban® 1 (Therban® 1707 S), with RDB of 3.6% and 34% acrylonitrile (ACN) was crosslinked using the following
two different efficient sulfur vulcanization systems:

EV1 TMTD 2 phr

CBS 0.5 phr
Sulfur 0.5 phr

EV2 TMTD 4 phr

Sulfur Donor 3 phr

For comparison, Therban® 1 was also crosslinked with 2,2’bis (tert-butylperoxy diisopropylbenzene) at 7 phr and
triallyl cyanurate (TAC) coagent at 1.5 phr.

Therban® 1 Compounds
Crosslinking Systems Peroxide EV1 EV2
Therban 1 (Therban 1707S now Therban C 3467)
® ® ®
100 100 100
MgO 2 2 2
Stearic Acid – 1 1
ODPA 1 1.5 1.5
ZnMMBI 0.4 2 2
N550 Carbon Black 45 45 45
TAIC [4] 1.5 – –
Bis(tert butylperoxy isopropyl)benzene (40%) [2] 7 – –
S – 0.5 –
TMTD – 2 4
Dithiodicaprolactam (80%) Sulfur Donor – – 3
CBS – 0.5 –
Parts by weight 158.9 156.5 160.5
Density (g/cm3) 1.16 1.14 1.14

Table 5 Therban® 1 Compounds

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Compound Properties
The crosslinking system EV1 results in rapid crosslinking with adequate processing safety. System EV2 is slower
but gives increased processing safety. (Table 6)

Therban® 1 Compound Properties

Crosslinking Systems Peroxide EV1 EV2
Therban 1 (Therban 1707S now Therban C 3467)
® ® ®
100 100 100
TMTD/CBS/S TMTD/S Donor
Mooney Viscosity 78 77 70
ML1+4 @ 120°C
Mooney Scorch
t5 @ 130°C (minutes) – 5 27
t5 @ 140°C (minutes) 14 – –
Vulkameter at 180°C 170°C 170°C
t50 (minutes) 4.2 2.9 6.3
Fmin. (N) 3 2.9 2.3
Fmax. (N) 59 44 46

Table 6 Therban® 1 Compound Properties

Properties of the Vulcanizates

Crosslink Density and Types
Peroxide cure results in carbon-carbon bridges, EV2 has a higher proportion of monosulfidic crosslinks, and EV1
has a greater portion of polysulfidic and some disulfidic and monosulfidic.

Physical Properties
All the crosslinking systems compared resulted in similar hardness levels (Table 7). Sulfur vulcanizates show
higher tensile strength; however, peroxide crosslinking gives better heat aging resistance as shown in Figure 7.
They also give considerably higher retention of elongation than the peroxide vulcanizate (Figure 7). The modulus
was higher for the peroxide vulcanizate.
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Therban® 1 Physical Properties

Crosslinking Systems Peroxide EV1 EV2
TMTD/CBS/S TMTD/S Donor
Vulcanization at 15 minutes, 180°C 15 minutes, 170°C 15 minutes, 170°C
Hardness (Shore A) 74 72 70
Tensile Strength (MPa) 24 32 31
Elongation at Break (%) 255 590 570
100% Modulus (MPa) 7.1 3.1 3
200% Modulus (MPa) 18.6 8.1 8.1
300% Modulus (MPa) – 14.7 13.5
Rebound Resilience at 23°C (%) 36 41 41
Tear Strength (ISO 34B/b) (N/mm) 12 27 26

Table 7 Therban® 1 Physical Properties

Retention of Elongation at Break

100
90
80
70
Elongation Retention (%)

60
50
40
30
20
10
0
Peroxide EV1 EV2
TMTD/CBS/S TMTD/S Donor
Figure 7 Retention of Elongation at Break After Aging 14 days @ 150°C

Compared to the peroxide vulcanizate, sulfur vulcanizates had, as expected, higher rebound resilience and
tear strength.
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of Therban HNBR Elastomers
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Compression Set
Compression set for sulfur and peroxide vulcanizates over a temperature range –10 to 150°C can be seen in Figure 8
(test time 70 hours, 25% deformation, ASTM D 395-85). At temperatures below room (23°C) the measurement was
performed at the storage temperature.

As expected, compression set is lower for the peroxide vulcanizate.

Compression Set vs. Temperature

Compression Set (70 hours) EV1

100 EV2

80
Compression Set (%)

60

40

20
Peroxide Cure

0
0 20 40 60 80 100 120 140 160
Temperature °C

Figure 8 Compression Set vs. Temperature: Therban® 1 Crosslinked with Peroxide, EV1 (TMTD/CBS/S) and EV2 (TMTD/S Donor)
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Therban® 1 Low Temperature Properties

Crosslinking Systems Peroxide EV1 EV2
TMTD/CBS/S TMTD/S Donor
Vulcanization at 15 minutes, 180°C 15 minutes, 170°C 15 minutes, 170°C
Glass Transition (°C) –11 –11 –11
ISO 2856
Brittleness Point Temperature (°C) <–70 <–70 <–70
ISO 812
Temperature Retraction at 50% Elongation, ISO 2921
TR 10 (°C) –22 –19 –21
TR 30 (°C) –18 –14 –17
TR 50 (°C) –15 –10 –13
TR 70 (°C) –12 –7 –9

Table 8 Therban® 1 Low Temperature Properties

Influence of Crosslinking System on TR Values

TR Gradations
-5

EV1
-10 EV2
Temperature (°C)

Peroxide Cure
-15

-20

-25
0 20 40 60 80

Figure 9 Influence of Crosslinking System on TR Values at 50% Elongation Therban® 1 Crosslinked with Peroxide, EV1
(TMTD/CBS/S) and EV2 (TMTD/S Donor)
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Low Temperature Properties (Figure 9)

As seen from Table 8, the influence of the crosslinking system is observed only in the temperature retraction test.
Other tests such as glass transition temperature, torsion pendulum, Gehman test and brittleness point test were not
able to distinguish between the crosslinking systems.

DeMattia Flex (Figure 10)

The flex-to-fatigue life cycle is strongly dependent on the type of crosslink system and crosslink density. The
polysulfidic crosslinks are flexible when compared to carbon-carbon and monosulfidic bridges. The EV1 system,
because of its polysulfidic crosslinks, shows better flex fatigue compared to peroxide and EV2 cure systems.

DeMattia Flex Test

Unaged (kilocycles)
3500
Aged (kilocycles)
3000

2500
Kilocycles

2000

1500

1000

500

0
Peroxide EV1 EV2

Figure 10 DeMattia Flex Test: Unaged vs Aged 7 days @ 150°C

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Effect of Coagents and Peroxide Crosslinking in HNBR

It is known that the coagents, being low molecular weight in comparison with the polymer, lower the compound
viscosity and improve processability. Four commercially available coagents were evaluated at equal parts by weight
and at equal equivalence level, using unsaturation as an indicator of the functionality. The formulation and physical
properties are shown in Tables 9a and 9b.

Effect of Coagents at Equal Parts by Weight

Coagents None TAC TAIC HVA No.2 SR 350
[4] [3] [5]
Therban 2 (Therban A 3407)
® ®
100
N550 Carbon Black 50
MgO 10
ZnO 3
Carnuba Wax 2
SDPA 1
ZnMMBI 1
Dicumyl Peroxide (40%) [1] 7
Coagent – 2.5 2.5 2.5 2.5
Compound Properties
Mooney Scorch
t5 @ 135°C (minutes) 16 17 17 5 4
t90 @ 177°C (minutes) 7.3 7.9 8.2 4.8 6.5
Physical Properties
Vulcanization for t90 @ 177°C
Hardness (Shore A) 76 74 75 78 76
Tensile Strength (MPa) 22.3 22.2 21.3 23.8 22.2
Elongation at break (%) 445 370 380 270 400
100% Modulus (MPa) 4.6 4.5 5 8.4 5.6
300% Modulus (MPa) 17.8 20.1 20.2 - 19.5
Die C Tear Strength (N/mm) 56 50 49 49 53
Compression Set, 70 hours @ 150°C
No Post Cure (%) 52 46 43 34 46
After Post Cure (16 hours @ 150°C) (%) 46 42 30 28 33

Table 9a Peroxide Crosslinking of Therban® 2 in Presence of a Coagent at Equal Parts (by weight) Level
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Effect of Coagents at Equal Equivalence Level

Coagents None TAC TAIC HVA No.2 SR 350
[4] [3] [5]
Therban 2 (Therban A 3407)
® ®
100
N550 Carbon Black 50
MgO 10
ZnO 3
Carnuba Wax 2
SDPA 1
ZnMMBI 1
Dicumyl Peroxide (40%) [1] 7
Coagent – 2.5 2.5 4 5.1
Compound Properties
Mooney Scorch
t5 @ 135°C (minutes) 16 17 17 4 4
t90 @ 177°C (minutes) 7.9 7.9 8.2 4.8 6.8
Physical Properties
Vulcanization for t 90 @ 177°C
Hardness (Shore A) 76 74 75 80 77
Tensile Strength (MPa) 22.3 22.2 21.3 23.2 21.9
Elongation at Break (%) 445 370 380 225 375
100% Modulus (MPa) 4.6 4.5 5 10.2 5.6
300% Modulus (MPa) 17.8 20.1 20.2 - 19.7
Die C Tear Strength (N/mm) 56 50 49 47 55
Compression Set, 70 hours @ 150°C
No Post Cure (%) 52 46 43 25 38
After Post Cure (16 hours @ 150°C) (%) 46 42 30 22 34

Table 9b Peroxide Crosslinking of Therban® 2 in Presence of a Coagent at Equal Equivalence Level (phr)

Compression set at equal parts by weight and equal equivalence level for the coagents was evaluated. The lowest
compression set is obtained with HVA No.2.

Considering scorch safety and physical properties, TAIC [4] offered the best balance in properties.
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Summary
Sulfur vulcanization was discovered in 1839, while peroxide cure was discovered in 1915. Versatile and successful
accelerator sulfenamides were introduced in 1932, while widely used dicumyl peroxide was introduced in 1955.
(Figure 11).

Advantages of sulfur vulcanization are delayed crosslinking resulting in a gain in processing time and excellent
dynamic properties. Advantages of peroxide vulcanization include low compression set and relatively better aging
resistance than sulfur cures.

Comparison of Sulfur vs. Peroxide Curing

1839 Goodyear discovered use of elemental sulfur 1915 Discovery of benzoyl peroxide
1932 Discovery of sulphenamides 1955 Dicumyl peroxide introduced
Vulcanizate Properties
Sulfur Cure Peroxide Cure
Advantages
• Delayed action, i.e., scorch safety • Low compression set
• Excellent dynamic performance ( – Sx –) • Low creep
• Better aging and hence high temperature use
• No staining with copper
Disadvantages
• Reversion tendency • Low tensile and tear strength
• High compression set • May or may not show delayed action, depending on
• Stains with copper (copper sulfides) type of peroxide and cure temperature
Both Cure Systems Are Complementary Rather Than Competitive

Figure 11 Comparison of Sulfur vs. Peroxide Curing

The disadvantages of sulfur vulcanization are that the compression set is high and staining occurs due to the
formation of copper sulfides. Disadvantages of peroxide vulcanizates are lower tensile and tear strength.

In conclusion, both crosslinking systems are complementary rather than competitive. Each one offers distinct
advantages and disadvantages.
Sulfur vs. Peroxide Crosslinking
®
of Therban HNBR Elastomers
Based on Lit. # FK-0447e
01.99
Page 19 of 20

Guidelines for Sulfur Vulcanization

Composition Trade Name Supplier
Polymer
Therban® 1 Hydrogenated nitrile rubber Therban® 1707 S Bayer
Now Therban® C 3467
Therban® 2 Hydrogenated nitrile rubber Therban® 1707 Bayer
Now Therban® A 3407
Antioxidants
OPDA Reaction product of diphenyl- Vulkanox® OCD Bayer
amine and diisobutylene
ZnMMBI Zinc salt of methylmercapto Vulkanox® ZMB 2 Bayer
benzimidazole
SDPA Styrenated diphenylamine Vulkanox® DDA Bayer
Cure Systems
CBS N-cyclohexal-2-benzothiazole Vulkacit® CZ Bayer
sulfenamide
TMTD Tetramethyl thiuram disulfide Vulkacit® Thiuram Bayer
Dithiodicaprolactam sulfur Rhenocure® S/G Rhein Chemie
donor, 80% active
Dicumyl Peroxide, 40% active Di-Cup® 40C Hercules[1]
Bis(t-butyl-peroxy) Vul-Cup® 40KE Hercules[2]
diisopropylbenzene, 40% active
Coagents
MPDM N,N’-m-phenylene dimaleimide HVA No. 2™ DuPont[3]
TAC Triallyl cyanurate, 70% active Rhenofit TAC/S
®
Rhein Chemie
TAIC Triallyl isocyanurate Diak No. 7 DuPont[4]
Trimethylolpropane SR 350™ Sartomer[5]
trimethacrylate

Table 10 Ingredients Used

 Sulfur vs. Peroxide Crosslinking
®
of Therban HNBR Elastomers
Based on Lit. # FK-0447e
01.99
Page 20 of 20

Registered Trademarks of Rhein Chemie Rheinau GmbH:

Rhenocure
Rhenofit

Bibliography
1. I. J. Sjothun and G. Alligner, in “Vulcanization of Elastomers,” I.J.Sjothun and G. Alligner, Ed., Reinhold Publishing,
New York, 1964, History and Technology of Elastomer Vulcanization.
2. N. Upadhyay, Technological Role of Vulkacit Accelerators, Internal Report, Bayer, 1988.
3. A. Coran, in “Science and Technology of Rubber,” F. R. Eirich, Ed., Academic Press, New York, 1978, Ch.7.
4. Morrison and M. Porter, Rubber Chem. & Technol., 57, 63 (1984).
5. Krebs, Gummi. Asbest., 8, 68 (1955).
6. J. Brydson, “Rubbery Materials and Their Compounds,” Elsevier Applied Science, New York, 1988.
7. U. Eisele, in “Introduction to Polymer Physics,” Springer Verlag, New York, 1990, p 53.

Acralen®, Baycoll®, Baypren®, Baystal®, Desmocoll®, Desmodur®, Disflamoll®, Dispercoll®, Emulvin®, Krylene®, Krynac®, Krynol®, Levapren®, Mesamoll®, Perbunan®, Polysplint®, Porofor®,
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