Accepted Manuscript

A novel system for measurement of types and densities of sulfur crosslinks of a filled
rubber vulcanizate

Sung-Seen Choi, Eunha Kim

PII: S0142-9418(14)00267-0
DOI: 10.1016/j.polymertesting.2014.12.007
Reference: POTE 4353

To appear in: Polymer Testing

Received Date: 31 October 2014

Accepted Date: 12 December 2014

Please cite this article as: S.-S. Choi, E. Kim, A novel system for measurement of types and
densities of sulfur crosslinks of a filled rubber vulcanizate, Polymer Testing (2015), doi: 10.1016/
j.polymertesting.2014.12.007.

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 ACCEPTED MANUSCRIPT

Test Method

A novel system for measurement of types and densities of sulfur

crosslinks of a filled rubber vulcanizate

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Sung-Seen Choi* and Eunha Kim

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Department of Chemistry, Sejong University, 209 Neungdong-ro, Gwangjin-gu,

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Seoul 143-747, Korea

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* Corresponding author.
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E-mail address: sschoi@sejong.ac.kr (S.-S. Choi)

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ABSTRACT

A novel system for measuring the crosslink densities of mono-, di- and polysulfides of a

filled rubber vulcanizate was developed. The system included pre-swelling, cleavage of

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sulfur crosslinks by a chemical probe using thiol/n-hexylamine instead of

thiol/piperidine, and two step swelling. A sample cage made of stainless steel mesh was

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used to measure multiple samples at the same time and to reduce experimental errors.

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The organic materials-extracted sample was pre-swollen in toluene to introduce the

probe chemicals more rapidly and homogeneously into the whole network. Polysulfidic

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crosslinkages were cleaved by a chemical probe of propane-2-thiol/n-hexylamine in
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toluene, while di- and polysulfidic crosslinkages were dissociated by a chemical probe

of n-hexanethiol/n-hexylamine in toluene. The experimental errors were lower than 2%.

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By using cubic apparent crosslink density, fractions of the crosslink types of an

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unknown rubber vulcanizate could be estimated even although the filler content and

rubber composition are not analyzed.

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Keywords: sulfur crosslink type, chemical probe, hexylamine, rubber vulcanizate, cubic
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apparent crosslink density

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1. Introduction

In general, rubber compounds are crosslinked by sulfur vulcanization1-3 or

peroxide curing4, with sometimes an alternative specific system such as resole curing5.

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Sulfur vulcanization is the most popular and makes varying crosslink types such as

mono-, di-, and polysulfides.3,6-9 Crosslink type and degree of crosslink density of a

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rubber vulcanizate determine the physical properties such as modulus, hardness,

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resilience, elongation at break, heat build-up, and so forth.9-13 By increasing crosslink

density, modulus, hardness, resilience and abrasion resistance increase, whereas

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elongation at break, heat buildup and stress relaxation decrease. Stress relaxation,
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tensile strength, and resilience increase in proportion to the di- and polysulfide content,

whereas fatigue and thermal aging resistances decrease.

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It is well known that crosslink density can be measured using swelling or solid
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state NMR.6-9,14-17 Crosslink density of each sulfur crosslink type is measured using a
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swelling method by dissociation of di- and polysulfidic linkages.6,8,9,18 Di- and

polysulfidic linkages are usually cleaved by thiol-amine chemical probes.18-21 In general,

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polysulfic crosslinks are dissociated using a chemical probe of propane-2-thiol (0.4 M)

and piperidine (0.4 M) in n-heptane, while di- and polysulfidic crosslinks are cleaved
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using a chemical probe of hexane-1-thiol (1 M) in piperidine.18-20 Kiroski et al.

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employed toluene instead of n-heptane as a carrier solvent for cleavage of sulfur

crosslinks of an unfilled acrylonitrile-butadiene rubber (NBR) vulcanizate and reported

that di- and polysulfidic crosslinks could be cleaved by treating with hexane-1-thiol (1

M) in piperidine for 72 h under nitrogen, while polysulfic crosslinks could be cleaved

by treating with propane-2-thiol (0.4 M) and piperidine (0.4 M) in toluene for 2 h.21

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It is well known that piperidine exhibits genotoxicity, reproductive toxicity and

teratogenicity. Hence, it is necessary to replace piperidine with another amine species.

In this study, n-hexylamine (C6H15N) was employed instead of piperidine (C5H11N).

The pKa values of piperidine and n-hexylamine are 11.12 and 10.56 at 25oC,

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respectively. The thiol chemicals have offensive odor and, especially, propane-2-thiol

has low boiling point (57 - 60oC) and relatively high vapor pressure (8.8 mmHg at 20oC,

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455 mmHg at 37.8oC). Hence, in this study, a closed equipment was used to prevent

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diffusion of vapors of amine and thiol chemicals into the air. A sample cage was made

and used to reduce experimental errors. A pre-swelling process before treatment with

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the chemical probe was employed for fast penetration of the probe chemicals into the
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inner part of the sample.

Generally, crosslink density of a cured rubber sample is measured by swelling

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and applying the Flory–Rehner equation.22-25 In order to calculate crosslink density,

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correction for the filler content and the rubber composition for interaction parameter are

needed. However, for unknown filled rubber vulcanizates, the filler content and rubber
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composition are not known. In the present work, for estimation of crosslink type
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fractions of an unknown rubber vulcanizate, a data analysis method adapting apparent

crosslink density (1/Q) is suggested. The filler content correction is not necessary to
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calculate the 1/Q value which is also not dependent on the rubber composition.
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2. Experimental

A silica/carbon black-reinforced SBR compound was composed of SBR 1789

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(Kumho Petrochemical Co.), silica (Z175 of Degussa Co., 50 phr), carbon black (N330,

10 phr), X50S (Evonik Ind., Si69/N330 = 50/50, 8 phr), processing oil (3 phr), stearic

acid (2 phr), ZnO (4 phr), wax (2 phr), HPPD (N-phenyl-N'-(l,3-dimethylbutyl)-p-

phenylenediamine, 2 phr), TBBS (N-tert-butyl-2-benzothiazole sulfenamide, 2 phr), and

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sulfur (1.5 phr). Mixing for master batch (MB) was performed using a kneader type

mixer and final mixing (FM) was performed using a two roll mill. The vulcanizate was

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prepared by curing the compound in a compression mold at 170oC for 30 min.

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Tetrahydrofuran (THF), n-hexane and toluene were purchased from Daejung

Chemicals & Metals Co. Propane-2-thiol and hexanethiol were purchased from Aldrich

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Co. Hexylamine was purchased from Alfa Aesar Co. Chemical probe solution for
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dissociation of polysulfidic crosslinkages was made of 0.40 M propane-2-thiol/0.40 M

hexylamine in toluene. Chemical probe solution for dissociation of di- and polysulfidic
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crosslinkages was made of 2.0 M hexanethiol/4.0 M hexylamine in toluene. Before

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soaking the samples in the chemical probe solution, pure nitrogen gas was injected to

purge moisture and oxygen.

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The sample was cut with dimention of 0.5 × 0.5 cm2 and thickness about 3 mm.
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Organic additives in the sample was removed by extracting with THF and n-hexane for

3 and 2 days, respectively, and it was then dried for 2 days at room temperature. The
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weight of the organic materials-extracted sample was measured. The sample cage had
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dimensions of 3 × 3 × 3 cm and was made of stainless steel wire mesh with wire

diameter of 0.3 mm, giving it resistance against organic solvents and being large enough

to accommodate the volume expansion of the swollen samples. The stainless steel wire

mesh was cut with a cross shape and the joint connections were tied with

polytetrafluoroethylene tape to make a cubic shape, as shown in Figure 1. The samples

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were put in the sample cage and three sample cages were put in an 1 L container. When

the container is filled with 800 mL of solution, nine samples can be measured at the

same time. Multiple measurements in one container at the same time reduces the

experimental errors. For measurement of total crosslink density, the sample cages were

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soaked in toluene for 2 days at room temperature and the weights of the swollen

samples were measured.

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Before treating the samples with the chemical probe solution, they were pre-

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swollen in toluene for 1 day in order to introduce the probe chemicals more rapidly and

homogeneously into the whole network. Solubility parameter of toluene closely matches

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that of SBR and toluene is generally used as a swelling solvent of an SBR
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vulcanizate.26,27 The pre-swollen samples were put into the chemical probe solution and

pure nitrogen gas was injected into the solution to give an inert atmosphere. The
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container was sealed with a cap equipped with two stopcocks to prevent the chemical
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vapors from spreading out, as shown in Figure 2.

For cleavage of the polysulfidic crosslinkages, the pre-swollen samples in

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cages were immersed in the chemical probe solution of propane-2-thiol/hexylamine for

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2 – 24 hr at room temperature (Figure 2). For dissociation of the di- and polysulfidic

crosslinkages, the pre-swollen samples in cages were immersed in the chemical probe
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solution of hexanethiol/hexylamine for 12 – 72 hr at room temperature. After the

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chemical probe treatment, they were immediately soaked in toluene for one day, then

moved to fresh toluene and again soaked for one day (Figure 2). After the second

swelling, the weights of the swollen samples were measured. The total experimental

procedure is illustrated in Figure 3.

Crosslink densities of the samples were obtained from the swelling data.22-24

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The crosslink densities (Xcs) were calculated using the Flory–Rehner equation25 (1)

Xc = -[ln(1 - ν2) + ν2 + χν22]/[V1(ν21/3 - ν2/2)] (1)

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where v2 is the volume fraction of the crosslinked polymer, χ is the interaction

parameter between the polymer and solvent, V1 is the molar volume of the swelling

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solvent. The v2 is obtained by equation (2)

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v2 = (m2/ρ2)/[(m2/ρ2) + (m1/ρ1)] (2)

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where m1 and m2 are the solvent and specimen weights at equilibrium swelling,

respectively, and ρ1 and ρ2 are the densities of swelling solvent and unswollen rubber
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vulcanizate, respectively. Densities of toluene (ρ1) and SBR (ρ2) are 0.865 and 0.953
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g/cm3, respectively. The V1 is 106.3 cm3/mole. The interaction parameter (χ) of SBR
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with toluene is 0.446 for emulsion SBR.27,28

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3. Results and Discussion

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Plausible mechanisms for cleavages of sulfur crosslinks by the chemical probes

are described in Scheme 1. Nucleophiles such as nitrogen, sulfur, and phosphorus

species interact with sulfur crosslinks to weaken the sulfidic bonds or to cleave sulfide

bridges.29-32 Thiol can react with a sulfur crosslink and open it by substitution reaction.

Combination of thiol and amine makes a complex such as hexylammonium propane-2-

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thiolate or hexylammonium hexanethiolate ion pair for propane-2-thiol/hexylamine or

hexanethiol/hexylamine system, respectively, in which nucleophilicity of the sulfur

atom is enhanced. This is capable of cleaving sulfur crosslinks. The propane-2-thiolate

ion can also react with disulfide to cleave it, although its rate can be expected to be very

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slow compared to dissociation of polysulfides. Hence, it is important to determine

suitable treatment time so as not to be over treated.

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After the chemical probe treatment, the treated samples were immediately

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transferred into the swelling solvent (toluene) and the container was sealed with a cap

(Figure 2). The samples were soaked in toluene for first 1 day, and then were transferred

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into the second toluene container and were swollen for another 1 day. During the first
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swelling, the probe chemicals remained in the sample were extracted. After the second

swelling, weights of the swollen samples were measured. As shown in equations (1) and
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(2), swollen volume of a sample is required for calculation of the Xc. The swelling ratio
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(Q) was calculated by the equation (3)

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Q = (Ws - Wu)/Wu (3)

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where Ws and Wu are the weights of the swollen and unswollen samples, respectively.
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The swelling ratios were summarized in Tables 1 and 2 for the chemical probes of
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propane-2-thiol/hexylamine and hexanethiol/hexylamine, respectively. The

experimental results show low relative errors below 2%. Experimental errors for the

dissociation of polysulfidic crosslinkages (using propane-2-thiol/hexylamine chemical

probe) were relatively smaller than those for the dissociation of di- and polysulfidic

crosslinkages (using hexanethiol/hexylamine chemical probe).

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Variations of the Xcs by the chemical probe treatment were plotted as a

function of the treatment time, as shown in Figure 4. The Xcs remarkably decreased in

the initial period and then slightly decreased with the treatment time, irrespective of the

chemical probe systems. For the hexanethiol/hexylamine system, the Xc steeply

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decreased until 12 hr and then slightly decreased. The notable Xc decrease in the initial

period means that hexanethiol and hexylamine easily penetrate into the inner region of

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the sample due to pre-swelling. The slight Xc decrease after 12 hr indicates that

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dissociation of remaining di- and polysulfides is proceeding and some of monosulfides

may also be cleaved. For the propane-2-thiol/hexylamine system, the Xc notably

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decreased up to 6 hr and then continuously decreased. The notable Xc decrease in the
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initial period also denotes that propane-2-thiol and hexylamine easily penetrate into the

inner region of the sample due to pre-swelling. The continuous Xc decrease after 6 hr
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might be due to dissociation of disulfide by propane-2-thiolate, as discussed previously.

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Decrement of the crosslink density (∆Xc) was obtaind using the equation (4).
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∆Xc (%) = 100×(Xci - Xcf)/Xci (4)

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where Xci and Xcf are the initial and final Xcs, respectively. The initial Xc is the total Xc
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and the final Xc indicates Xc after the chemical probe treatment. Figure 5 shows
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variations of ∆Xc with treatment time. For the hexanethiol/hexylamine system, ∆Xc after

12 hr was more than 80%. This means that the fraction of the monosulfide crosslink of

the total crosslink is less than 20%. After the notable ∆Xc in the initial period, ∆Xc

continuously increased. This phenomenon was particularly apparent in the propane-2-

thiol/hexylamine system. Considering the relative unstability of disulfide crosslinks

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compared to monosulfidic crosslinks,33 it may be that the optimal treatment time for the

propane-2-thiol/hexylamine system is about 6 hr, after which the steep decrement is

moderated. Since it is not possible to prevent unexpected disulfide dissociation, it is

necessary to control the treatment time by considering the slope change of the

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decrement plot. For the propane-2-thiol/hexylamine system, the ∆Xc rates were 7.13,

1.12, and 0.68 %/hr for the first 6 hr (0 – 6 hr), second 6 hr (6 – 12 hr), and next 12 hr

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(12 – 24 hr), respectively. Since the ∆Xc rate for the first period was much greater than

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the others, the optimal treatment time of propane-2-thiol/hexylamine system could be 6

hr. For the hexanethiol/hexylamine system, the ∆Xc rates were 6.78, 0.28, 0.14, and

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0.07 %/hr for the first 12 hr (0 – 12 hr), second 12 hr (12 – 24 hr), next 24 hr (24 – 48
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hr), and final 24 hr (48 – 72 hr), respectively. The ∆Xc rate for the first period was much

greater than the others. For the hexanethiol/hexylamine system, considering the time
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required to dissociate disulfides, the optimal treatment time could be 48 hr. By applying
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the optimal treatment times, percentages of the mono-, di-, and polysulfide crosslinks of
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the SBR vulcanizate are about 12, 45, and 43%, respectively.

In order to obtain Xc, not only the sample weight at equilibrium swelling but
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also the χ value is required. For analysis of unknown samples, it is possible to obtain

proper χ values if the type and composition of rubber is known. The filler content
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should be determined to obtain the v2 value by correction of the filler content. Filler
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content of an unknown filled rubber vulcanizate can be determined by TGA

analysis,34,35 but it is very hard work to determine the exact rubber composition. The Xc

value is dependent on the v2 value which linearly increases with the sample weight at

equilibrium swelling, as shown in equations (1) and (2). Hence, the Q value is closely

related to the Xc value, and the reciprocal swelling ratio (1/Q) is generally used as the

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apparent crosslink density.22,23

The 1/Q was plotted as a function of the treatment time, as shown in Figure 6.

Like the Xc variation, 1/Q decreased considerably and then slightly decreased as the

treatment time increased (Figure 6). Figure 7 shows variations of the 1/Q decrement

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with the treatment time and it has similar trends to the ∆Xc variations of Figure 5.

However, there is a big difference in the variation range. For the 1/Q decrement

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variations (Figure 7), the variation ranges were 10 – 30% and 40 – 60% for the propane-

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2-thiol/hexylamine and hexanethiol/hexylamine systems, respectively. For the ∆Xc

variations (Figure 5), the variation ranges were 10 – 60% and over 80% for the propane-

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2-thiol/hexylamine and hexanethiol/hexylamine systems, respectively.
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In order to obtain the Xc of a filled rubber vulcanizate, the filler content and the

interaction parameter must be known as well as the ν2 and V1 values, as discussed above.
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For an unknown filled rubber vulcanizate, the filler content and rubber composition
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have to be precisely analyzed to calculate the Xc. It is very valuable and useful to find a
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factor to estimate the crosslink density decrement by cleavage of sulfur crosslinks

instead of the Xc of equation (1).

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Since the ν2 and χ values are less than 1.0, equation (1) can be simply written

as equation (5).
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Xc ≈ -[ln(1 - ν2) + ν2]/(V1 ν21/3) (5)

Hence, ∆Xc can be simply written as equation (6).

∆Xc (%) = 100×(Xci - Xcf)/Xci

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= 100×{-[ln(1 - ν2i) + ν2i]/(V1 ν2i1/3) - -[ln(1 - ν2f) + ν2f]/(V1 ν2f1/3)}/{-[ln(1 - ν2i) + ν2i]/(V1 ν2i1/3)}

= 100×{-[ln(1 - ν2i) + ν2i]/ν2i1/3 + [ln(1 - ν2f) + ν2f]/ν2f1/3}/{-[ln(1 - ν2i) + ν2i]/ν2i1/3} (6)

According to equation (6), ∆Xc is not dependent on V1. In order to examine relation

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between v2 and 1/Q, equations (2) and (3) are rewritten as follow:

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v2 = (m2/ρ2)/[(m2/ρ2) + (m1/ρ1)] = 1/[1 + (m1/ρ1)/(m2/ρ2)] (7)

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1/Q = Wu/(Ws - Wu) = [(m2 + mf + m1) - (m2 + mf)]/(m2 + mf) = m1/(m2 + mf) (8)

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Comparing equations (7) and (8), v2 has an inversely proportional relation to m1,
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whereas 1/Q is proportional to m1. The ∆Xc value has an inversely proportional relation

to ν21/3 in equation (6). Hence, cubic apparent crosslink density, (1/Q)3, could be applied
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to estimate fractions of the crosslink types of an unknown filled rubber vulcanizate,

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since it does not include ν2, V1, and χ.

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Decrement of the cubic apparent crosslink density, ∆(1/Q)3 is defined by

equation (9).
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∆(1/Q)3 (%) = 100×[(1/Q)3i – (1/Q)3f]/(1/Q)3i (9)

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where (1/Q)3i and (1/Q)3f are the initial and final (1/Q)3s, respectively. Figure 8 shows

the ∆(1/Q)3 variation with the treatment time. The ∆(1/Q)3 variation is nearly the same

as that of ∆Xc in Figure 5. In order to compare the ∆Xc and ∆(1/Q)3 variations in detail,

their values are listed in Table 3. Difference between the ∆Xc and ∆(1/Q)3 values is less

than 2%. Therefore, fractions of the crosslink types of unknown rubber vulcanizates

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could be estimated by ∆(1/Q)3 even if the filler content and rubber composition are not

known or are not analyzed.

4. Conclusions

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Characteristics of a novel analysis system for measurement of fractions of the

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mono-, di-, and polysulfide crosslinks are (1) using hexylamine instead of toxic

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piperidine, (2) using toluene as solvent, (3) sample cage made of stainless steel wire

mesh, (4) multiple measurements to reduce the experimental errors and to enhance the

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analysis efficiency, (5) pre-swelling procedure to introduce the probe chemicals more
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rapidly and homogeneously into the whole network, (6) a closed equipment to prevent

the amine and thiol vapors from spreading out into the air, (7) two swelling steps to
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remove the probe chemicals remaining in the sample, and (8) a data analysis method for
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an unknown rubber vulcanizate by employing cubic apparent crosslink density. The

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experimental errors were lower than 2%. The ∆(1/Q)3 variation was nearly the same to

that of ∆Xc, and the differences between the ∆Xc and ∆(1/Q)3 values were less than 2%.
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Fractions of the crosslink types of unknown rubber vulcanizates could be estimated by

∆(1/Q)3.
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CRC Press, Boca Raton, 2007.

[28] J. S. Deng, I. Isayev, Injection molding of rubber compounds: Experimentation and

simulation, Rubber Chem. Technol. 64 (1991) 296.

[29] R. E. Humphrey, J. L. Potter, Reduction of disulfides with triphenylphosphine,

Anal. Chem. 37 (1965) 164.

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[30] L. E. Overman, E. M. O'Connor, Nucleophilic cleavage of the sulfur-sulfur bond

by phosphorus nucleophiles. IV. Kinetic study of the reduction of alkyl disulfides

with triphenylphosphine and water, J. Am. Chem. Soc. 98 (1976) 771.

[31] C. K. Das, S. Banerjee, Studies on diphenylguanidine–accelerated sulfur

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vulcanization of styrene butadiene rubber in the presence and absence of

dicumylperoxide, J. Polym. Sci.: Polym. Chem. Ed. 16 (1978) 2971.

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[32] S.-S. Choi, Influence of thermal aging on change of crosslink density and

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deformation of natural rubber vulcanizates, Bull. Korean Chem. Soc. 21 (2000)

628.

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[33] S.-S. Choi, Bond dissociation of sulfur crosslinks in IR and BR vulcanizates using
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semi-empirical calculations, Kor. Polym. J. 5 (1997) 39.

[34] S.-S. Choi, H. Kim, J. I. Kim, H. R. Cho, D. K. Oh, Analysis of unbound materials
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in carbon black-filled NR vulcanizates, J. Appl. Polym. Sci. 71 (1999) 1995.

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[35] M. J. Fernandez-Berridi, N. Gonzalez, A. Mugica, C. Bernicot, Pyrolysis-FTIR and

TGA techniques as tools in the characterization of blends of natural rubber and

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SBR, Thermochimica Acta, 444 (2006) 65.

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List of Tables

Table 1. Swelling ratios of the rubber vulcanizate after cleavage of polysulfidic

crosslinks by treatment of propane-2-thiol/hexylamine chemical probe.

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Table 2. Swelling ratios of the rubber vulcanizate after cleavage of di- and polysulfidic

crosslinks by treatment of hexanethiol/hexylamine chemical probe.

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Table 3. Decrements of the crosslink densities (Xcs) and cubic apparent crosslink

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densities [(1/Q)3s] with the chemical probe treatment time (%).

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List of Figures

Fig. 1. Photograph of the sample cage made of stainless steel wire mesh and the

samples contained in a container of 1.0 L. The sample cage dimension is 3 × 3 × 3 cm3.

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Fig. 2. Photograph of (a) samples in the chemical probe solution (thiol/hexylamine) and

(b) samples in the swelling solvent (toluene). The container containing the chemical

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probe solution is sealed with a cap eqipped with two stopcocks for inert atmosphere.

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The container containing the swelling solvent is sealed with a cap.

Fig. 3. Experimental procedure for the measurement of types and densities of sulfur

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crosslinks.
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Fig. 4. Variation of the crosslink density (Xc) with the chemical probe treatment time.

Squares and circles denote the chemical probe solutions of propane-2-thiol and
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hexanethiol, respectively.
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Fig. 5. Variation of the decrement of crosslink density (Xc) with the chemical probe
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treatment time. Squares and circles denote the chemical probe solutions of propane-2-

thiol and hexanethiol, respectively.

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Fig. 6. Variation of the apparent crosslink density (1/Q) with the chemical probe

treatment time. Squares and circles denote the chemical probe solutions of propane-2-
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thiol and hexanethiol, respectively.

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Fig. 7. Variation of the decrement of apparent crosslink density (1/Q) with the chemical

probe treatment time. Squares and circles denote the chemical probe solutions of

propane-2-thiol and hexanethiol, respectively.

Fig. 8. Variation of the decrement of cubic apparent crosslink density [(1/Q)3] with the

chemical probe treatment time. Squares and circles denote the chemical probe solutions

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of propane-2-thiol and hexanethiol, respectively.

Scheme 1. Dissociation of sulfur crosslinks by chemical probes of propane-2-thiol,

hexanethiol, and hexylamine.

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Table 1. Swelling ratios of the rubber vulcanizate after cleavage of polysulfidic

crosslinks by treatment of propane-2-thiol/hexylamine chemical probe.

Treatment time (h) Swelling ratio (Q) Relative error (%)

0 2.44 ± 0.01 0.4

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2 2.78 ± 0.02 0.7
3 2.83 ± 0.03 1.1

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4 2.85 ± 0.01 0.4
6 2.94 ± 0.01 0.3

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12 3.06 ± 0.03 1.0
24 3.25 ± 0.02 0.6

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Table 2. Swelling ratios of the rubber vulcanizate after cleavage of di- and polysulfidic

crosslinks by treatment of hexanethiol/hexylamine chemical probe.

Treatment time (h) Swelling ratio (Q) Relative error (%)

0 2.44 ± 0.01 0.4

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12 4.28 ± 0.03 0.7
24 4.57 ± 0.07 1.5
48 4.95 ± 0.07 1.4

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72 5.14 ± 0.09 1.8

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Table 3. Decrements of the crosslink densities (Xcs) and cubic apparent crosslink

densities [(1/Q)3s] with the chemical probe treatment time (%).

Treatment time (h) ∆Xc ∆(1/Q)3 Difference (%)*

Propane-2-thiol/hexylamine system

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2 32.65 32.30 1.1
3 36.08 36.18 -0.3

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4 37.77 37.26 1.4
6 42.84 42.97 -0.3
12

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49.45 49.27 0.4
24 57.57 57.61 -0.1

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Hexanethiol/hexylamine system
12 81.36 81.41 -0.1
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24 84.69 84.76 -0.1
48 88.06 88.04 0.0
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89.75 89.24 0.6

*
Difference (%) = 100×[∆Xc - ∆(1/Q)3]/∆Xc
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Fig. 1. Photograph of the sample cage made of stainless steel wire mesh and the

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samples contained in a container of 1.0 L. The sample cage dimension is 3 × 3 × 3 cm3.

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Fig. 2. Photograph of (a) samples in the chemical probe solution (thiol/hexylamine) and

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(b) samples in the swelling solvent (toluene). The container containing the chemical
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probe solution is sealed with a cap eqipped with two stopcocks for inert atmosphere.

The container containing the swelling solvent is sealed with a cap.

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Fig. 3. Experimental procedure for the measurement of types and densities of sulfur

crosslinks.

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Propane-2-thiol
Hexanethiol
Crosslink density (10 mol/cm )

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3

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-5

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4

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2

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0 20 40 60 80
Treatment time (hr)
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Fig. 4. Variation of the crosslink density (Xc) with the chemical probe treatment time.
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Squares and circles denote the chemical probe solutions of propane-2-thiol and
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hexanethiol, respectively.
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100
Decrement of crosslink density (%)

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80

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60

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Propane-2-thiol
40
Hexanethiol

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0 20 40 60 80
Treatment time (hr)
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Fig. 5. Variation of the decrement of crosslink density (Xc) with the chemical probe
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treatment time. Squares and circles denote the chemical probe solutions of propane-2-
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thiol and hexanethiol, respectively.

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0.4 Propane-2-thiol
Apparent crosslink density (1/Q)

Hexanethiol

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0.3

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0.2

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Treatment time (hr)
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Fig. 6. Variation of the apparent crosslink density (1/Q) with the chemical probe
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treatment time. Squares and circles denote the chemical probe solutions of propane-2-
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thiol and hexanethiol, respectively.

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Decrement of apparent crosslink density (%)

60

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40

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20
Propane-2-thiol
Hexanethiol

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Treatment time (hr)
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Fig. 7. Variation of the decrement of apparent crosslink density (1/Q) with the chemical
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probe treatment time. Squares and circles denote the chemical probe solutions of
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propane-2-thiol and hexanethiol, respectively.

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100
Decrement of cubic apparent crosslink density (%)

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80

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60

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40 Propane-2-thiol
Hexanethiol

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0 20 40 60 80
Treatment time (hr)
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Fig. 8. Variation of the decrement of cubic apparent crosslink density [(1/Q)3] with the
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chemical probe treatment time. Squares and circles denote the chemical probe solutions
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of propane-2-thiol and hexanethiol, respectively.

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Sx NR3 Sx Sx NR3
NR 3
Sy Sy Sy

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H
Sx RSH Sx S xH

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Sy Sy SySR

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H3 C 6H 13
Sx Sx N SxH
H7C3SH-H2NC6H13

Sy Sy S SySC3 H7

C3 H7

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H3 C 6H 13
Sx Sx N SxH
H13C6SH-H2NC6H13

Sy Sy S SySC6 H13

C6 H13
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Scheme 1. Dissociation of sulfur crosslinks by chemical probes of propane-2-thiol,

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hexanethiol, and hexylamine.

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