Hindawi Publishing Corporation

ISRN Polymer Science

Volume 2013, Article ID 340426, 9 pages
http://dx.doi.org/10.1155/2013/340426

Research Article
Biodiesel as a Plasticizer of a SBR-Based Tire Tread Formulation

Franco Cataldo,1,2,3 Ornella Ursini,4 and Giancarlo Angelini4

1
Dipartimento di Scienze Ecologiche e Biologiche, Università della Tuscia, Largo Università snc, 01100 Viterbo, Italy
2
Soc Lupi Chemical Research srl, Via Casilina 1626A, 00133 Rome, Italy
3
University of Rome Tor Vergata, Via della Ricerca Scientifica, 00133 Rome, Italy
4
Istituto di Metodologie Chimiche, CNR, Via Salaria Km 29,300, Monterotondo Stazione, 00016 Rome, Italy

Correspondence should be addressed to Franco Cataldo; [email protected]

Received 25 January 2013; Accepted 17 February 2013

Academic Editors: T. R. Chantara, S.-H. Jafari, G.-H. Kim, B. Kiskan, and G. Lapienis

Copyright © 2013 Franco Cataldo et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

The solubility parameter of a series of methyl esters of fatty acids, the components of biodiesel, was calculated using the group
incremental method proposed by Van Krevelen. The solubility parameter of biodiesel was compared with that of a series of rubbers
like EPDM, butyl rubber, polyisoprene, polybutadiene, SBR (with different content of styrene), and nitrile rubber (with different
content of acrylonitrile) showing that biodiesel is an effective solvent of all the above mentioned rubbers with the exclusion of
nitrile rubber. Indeed, it was experimentally verified that polyisoprene, polybutadiene and SBR are easily soluble in biodiesel while
polystyrene gives a cloudy solution. Considerations on the solubility parameter of the biodiesel and of a series of rubbers have led
to the conclusion that biodiesel behaves essentially as an internal lubricant in a diene rubber matrix, the same situation occurs with
the common aromatic mineral oil plasticizer known as T-RAE. The experimental evaluation of biodiesel as plasticizer in an SBR-
based rubber compound in comparison to an aromatic mineral oil have led to the primary conclusion that biodiesel is reactive with
the sulphur curing agent subtracting sulphur to the crosslinking polymer chains and leading to a vulcanizatewith lower moduli,
tensile and hardness and higher elongations in comparison to a reference compound fully plasticized with an aromatic mineral oil.
However, biodiesel seems a good low temperature plasticizer because the low elastic modulus observed is desired in a winter tire
tread for a good grip on snow and ice. The present work is only an exploratory work, and the tire tread formulation with biodiesel
was not optimized.

1. Introduction predominantly composed by cycloaliphatic rings of various

types with some aromatic and aliphatic substituent. Thus,
Typical plasticizers of rubber compounds are aromatic, naph- in this case the core of the molecule is represented by
thenic or paraffinic oils. These plasticizers are obtained from the cycloaliphatic moiety. Finally, the aliphatic plasticizer
the processing of petroleum fractions, and they have not is essentially paraffinic in its nature, but its molecule is
an univocal chemical structure but are mixtures of complex still composed also by a minor component of aromatic and
molecules of relatively high molecular weight. For example, naphthenic nature [1]. The molecular weight of an aromatic
a plasticizer is defined aromatic because in its “average” plasticizer is about 550 Dalton followed by the molecular
molecule is made predominantly by aromatic hydrocarbons weight of a naphthenic plasticizer which is reported at
intended as benzenoid or polycyclic aromatic moieties. Such about 440 Dalton and the lightest “average” molecule is
aromatic moieties may represent the “core” of the “average” represented by the paraffinic plasticizer at about 350 Dalton
plasticizer molecule, and such “core” is functionalized by [1]. The molecular geometry also affects the glass transition
alkyl and naphthenic substituents. The aliphatic side chains temperature (𝑇𝑔 ) of the plasticizers, and consequently, the
and the naphthenic moieties (intended, e.g., as a cyclopen-
tane, cyclohexane, decalin rings attached to the aromatic 𝑇𝑔 of the aromatic plasticizer can be found at −38∘ C while
“core”) represent the minor component of the aromatic the naphthenic plasticizer 𝑇𝑔 = −72∘ C and the 𝑇𝑔 for the
plasticizer molecule. Conversely, a naphthenic plasticizer is paraffinic plasticizer can be down to −110∘ C [1]. The solubility
2 ISRN Polymer Science

of the plasticizer in a given rubber matrix is extremely −15∘ C and by an iodine number of 115 g/100 g. It was synthe-
important for the final properties of a rubber vulcanizate [2]. sized in the Actinium srl laboratory. The aromatic mineral oil
In the present work, we will discuss the solubility of the just plasticizer was a commercially available plasticizer known as
mentioned conventional plasticizers in a series of common T-RAE (Treated Residual Aromatic Extract).
rubbers used for tires and other rubber goods manufacture
such as conveyor belts and shoe soles in terms of solubility 2.2. Mixing and Testing. The formulation where the two
parameter and the resulting effects in viscoelastic properties plasticizers were tested was a standard tire tread formulation
of the vulcanizate. Furthermore, we will introduce a new composed by 137.5 phr of oil extended solution styrene-
“green” plasticizer consisting in a mixture of methyl esters of butadiene copolymer (S-SBR) having 18% of bound styrene
fatty acids derived from rapeseed oil and commonly known and 15% of vinyl groups. Carbon black N234 was used
as biodiesel, and we will test such a plasticizer in a standard as filler (88 phr) and the free plasticizer added to the
rubber compound for a tire tread application. formulation (either T-RAE or biodiesel) was 18 phr. Other
Biodiesel is commonly obtained from the transesterifi- components are stearic acid: 1.5 phr, ZnO 3.5: phr, paraf-
cation of rapeseed or canola oil with methanol [8–11]. Of fin wax: 1 phr, antidegradant 6PPD (N-1,3-dimethylbutyl-
course, other oils can be used such as palm oil, soybean N-phenyl-p-phenylenediamine): 1 phr, MBTS (mercaptoben-
oil, and other fats of vegetal or even animal origins and zothiazole disulphide): 1 phr, TBBS (t-butyl benzothiazyl
can be transesterified not only with methanol but also with sulphenamide): 1 phr, and soluble sulphur: 2.7 phr. The com-
higher aliphatic alcohols [12]. Biodiesel is produced as a pounds were prepared in two mixing stages. In the first
vegetable fuel for diesel engines but because of its increasing mixing stage, all ingredients were added with the exception of
availability and competitive price it could be used as a plas- sulphur, MBTS, and TBBS. In the second stage of mixing also
ticizer and lubricant for rubber and plastics compounding the curatives were added. The vulcanization was conducted
in a laboratory curing press at 160∘ C for 15 minutes.
with the advantage of using a raw material from renewable
Rheometer curves, Mooney viscosity, and Mooney scorch
sources which is also environmentally compatible in terms
as well as the measurement of the tensile strength and the
of biodegradability. The idea is not completely new, since
moduli were made according to standard tests procedures
we can find traces of this application of fatty acids esters as following ASTM or ISO standard practice.
plasticizer in the literature of the seventies of the last century The dynamic properties were measured on a mechani-
[13], but the interest increased dramatically in more recent cal spectrometer under temperature sweep conditions from
times as testified by patents [14, 15] and works in the open −30∘ C to +80∘ C on a strip of rubber specimen under 1% strain
scientific literature [16–19]. Although vegetable oils have been and 80 Hz.
occasionally used in the past at additives in plastics and
rubbers, in this work, we are focusing our attention on the 2.3. Experimental Solubility Test. Polyisoprene (200 mg) was
methyl esters of fatty acids. In the previous paragraphs, we stirred with 24 mL of biodiesel in a glass vial with screw
have reported the low temperature behavior of the plasticizers cap at 80∘ C. The complete dissolution of polyisoprene was
derived from mineral oil. The low temperature properties observed after 5 h. The same experiment was repeated with
of a plasticizer are of paramount importance also in the a sample of 200 mg of polybutadiene and 24 mL of biodiesel
low temperature behavior of the compounds where a given under identical conditions. The complete dissolution of
plasticizer is used. Lower congealing point plasticizers give polybutadiene was reached in 4 h. Also 200 mg of SBR (S1500
best low temperature flexibility to the rubber matrix where type) is soluble in biodiesel under the just described testing
they are hosted. Concerning the biodiesel, the fatty acids conditions. Finally, 75 mg of polystyrene is also soluble in
methyl esters with highest unsaturation are those with the 24 mL of biodiesel under the reported testing conditions but
lowest melting point. For example, methyl linolenate (3 the solution remains somewhat cloudy.
double bonds) has a melting point of −57∘ C followed by
methyl linoleate (2 double bonds) melting at −35∘ C and by
methyl oleate (1 double bond) with a melting point of −19∘ C. 3. Results and Discussion
The fully saturated methyl stearate melts at +40∘ C.
3.1. The Solubility Parameter. The solubility parameter has
It is worth mentioning here that castor oil is used in been defined by Brydson [2] as
the formulation of butyl rubber compounds, epoxidized
0.5
linseed oil is widely used in plastics and rubber as plasticizer (Δ𝐻vap − 𝑅𝑇)
and heat stabilizer, and vulcanized vegetable oils (known as 𝛿=[ ] . (1)
factices) are used for long time in elastomers to ensure low 𝑉𝑚
temperature flexibility and low hardness [2]. The evaporation enthalpy Δ𝐻vap was taken as the parameter
of the cohesion energy between molecules minus the thermal
energy needed to separate them (RT) divided by the molar
2. Experimental volume 𝑉𝑚 . Equation (1) can be rewritten as
2.1. Materials Used. The biodiesel used in the present work 0.5
(𝐸coh )
was obtained from the transesterification with methanol of 𝛿=[ ] . (2)
rapeseed oil and was characterized by a congealing point of 𝑉𝑚
ISRN Polymer Science 3

The cohesive energy 𝐸coh of a substance in a condensed state the calculated solubility parameters of several vegetable oils.
is defined as the increase in internal energy Δ𝑈 per mole of The data are compared with some solubility parameter taken
substance if all the intermolecular forces are eliminated. from the literature. The 𝛿𝑡 value calculated by Cataldo [3]
Hansen [6] has shown that the solubility parameter for olive oil 16.9 MPa1/2 is in good agreement with the value
proposed by Hildebrand and Scott does not take into account reported by Vaughan [4]. Instead, for linseed oil the 𝛿𝑡 value
the contribution of polar forces and hydrogen bonding; obtained by Cataldo [3] appears in line with all the other
therefore, a more complex solubility parameter has been vegetable oils, that is, 16.4 MPa1/2 , and in this context, it
proposed: appears surprisingly lower than the 𝛿𝑡 = 14.8 MPa1/2 found
by Vaughan [4] for the same vegetable oil. Indeed, Cataldo
𝛿2 = 𝛿𝑑2 + 𝛿𝑝2 + 𝛿ℎ2 , (3) has shown that 𝛿𝑡 for all the vegetable oils considered
derived from the contribution of three components of the is comprised between 16.2 and 16.9 MPa1/2 , and hence, it
cohesive energy: appears anomalous the 𝛿𝑡 = 18.0 MPa1/2 reported in [5] for
the brassica or rapeseed oil. The correct value of the solubility
𝐸coh = 𝐸𝑑 + 𝐸𝑝 + 𝐸ℎ , (4) parameter for brassica oilseed should be 𝛿𝑡 = 16.9 MPa1/2 .
The solubility parameter of the methyl esters of erucic acid,
respectively, due to the contribution of dispersion and polar oleic acid, linoleic acid, stearic acid, and palmitic acid was
forces plus a hydrogen bonding contribution. made using (6)–(9) and the tabulated values of 𝜑𝑑 , 𝜑𝑝 , and
It is possible to calculate the solubility parameter and the 𝐸ℎ as reported by Van Krevelen [21]. The density values of the
solubility parameter components of almost all molecules and methyl esters were taken from the literature [8, 9, 22]. The
polymers by a group contribution method [20, 21]. For this resulting solubility parameters are reported in Table 1. The
purpose, as explained by Van Krevelen [21], it is useful to 𝛿𝑡 values of the methyl esters considered as components of
introduce the molar attraction constant simply defined as biodiesel are practically identical and comprised in the range
0.5 between 16.6 and 16.7 MPa1/2 . Consequently, the solubility
𝜑 = (𝐸coh 𝑉𝑚 ) . (5) parameter of biodiesel is necessarily in this range, since the
A set of equations has been proposed by Van Krevelen [21] for biodiesel is composed exclusively by a mixture of methyl
the calculation of the solubility parameter components using esters of fatty acids. Other authors [7] have reported a slight
the molar attraction by a group contribution methodology: higher value for the solubility parameter of biodiesel as shown
in Table 1.
(∑ 𝜑𝑑 )
𝛿𝑑 = , (6) 3.3. The Solubility Parameter of Rubbers and Mineral Oil
𝑉𝑚
Plasticizers. In Table 2, the solubility parameters of a series of
0.5 common rubbers are reported. Large part of the values were
(∑ 𝜑𝑝2 )
𝛿𝑝 = , (7) taken from [2]. In the case of the “styrene-butadiene copoly-
𝑉𝑚 mers, the solubility parameter was estimated according to the
following:
∑ 𝐸ℎ 0.5
𝛿ℎ = [ ] . (8) 𝑋styrene 𝛿𝑡 PS + 𝑋butadiene 𝛿𝑡 BR = 𝛿𝑡 SBR copolymer , (10)
𝑉𝑚
where 𝑋styrene and 𝑋butadiene are the weight fractions of
The total solubility parameter can be calculated as follows:
these components in the copolymer and 𝛿𝑡 PS and 𝛿𝑡 BR
0.5 are the solubility parameters of pure polystyrene and pure
𝛿𝑡 = (𝛿𝑑2 + 𝛿𝑝2 + 𝛿ℎ2 ) . (9) polybutadiene used in the copolymer. Similarly, for the nitrile
rubber use was made of the analogous relationship:
It can be observed from (8) that the hydrogen bond parameter
𝛿ℎ cannot be calculated from the molar attraction, but directly 𝑋acrylonitrile 𝛿𝑡 ACN + 𝑋butadiene 𝛿𝑡 BR = 𝛿𝑡 Nitrile copolymer, (11)
from the hydrogen bonding energy 𝐸ℎ [21]. where 𝑋acrylonitrile and 𝑋butadiene are the weight fractions
of these components in the copolymer and 𝛿𝑡 ACN and 𝛿𝑡 BR
3.2. The Solubility Parameter of Fatty Acid Glycerides and are the solubility parameters of pure polystyrene and pure
Methyl Esters. In a previous work, Cataldo [3] has calculated polybutadiene used in the copolymer.
the solubility parameter of a series of vegetable oils as In [2], the solubility parameters of an aromatic and
triglycerides of fatty acids using the group increment method paraffinic oil plasticizers are also reported, as shown in
proposed by Van Krevelen [21] using (6)–(9). The calculation Table 2. However, the solubility parameters are too close,
procedure involved as a first step the calculation of the each other and do not reflect the real chemical and physical
solubility parameter of a single triglyceride of a given fatty difference among the two oils. Therefore, we have recalculated
acid, and then, knowing the fatty acids composition of a given the solubility parameter of these oils and also of naphthenic
oil, the following step was to proceed with the calculation oil according to the following considerations.
of the solubility parameter of the vegetable oil considering
the molar fraction of each fat in the vegetable oil. The (a) Paraffinic Oil. It is essentially made of linear and branched
details of the calculations are reported in [3]. Table 1 shows paraffin chains which represent about 70% of the total carbon
4 ISRN Polymer Science

Table 1: Solubility parameter of vegetable oils and methyl esters of the naphthenic molecules may represent 20% of the total
fatty acids. carbon atoms. The aromatic carbon atoms are only 10% of the
paraffinic oil and are represented by the benzene molecule
𝛿𝑡 in MPa1/2
with 𝛿𝑡 = 18.5 MPa1/2 [6]. Then, the solubility parameter
Olive oil [3] 16.9
calculation of the paraffinic oil is quite straightforward
Olive oil [4] 16.1 according to
Soybean oil [3] 16.2
Sunflower oil [3] 16.7 (0.7 × 12.8) + (0.2 × 16.8) + (0.1 × 18.5) = 14.2 MPa1/2 .
Peanut oil [3] 16.1 (12)
Linseed oil [3] 16.4
Linseed oil [4] 14.8 (b) Naphthenic Oil. It is essentially made a “core” of naph-
Brassica or rapeseed oil [3] 16.9 thenic rings which are well represented by cyclohexane whose
Brassica or rapeseed oil [5] 18.0 solubility parameter is 16.8 MPa1/2 [6], representing about
Glyceryl trioleate [3] 16.9 45% of the total carbon content. The paraffinic part of the
molecule represents about 35% of the total carbon atoms
Glyceryl tristearate [3] 17.7
which may be best represented by neopentane which has a
Castor oil [3] 18.3
solubility parameter of 12.8 MPa1/2 [2]. The aromatic carbon
Methyl erucate (this work) 16.6
atoms are about 20% of the naphthenic oil and are represented
Methyl oleate (this work) 16.7
by the benzene molecule with 𝛿𝑡 = 18.5 MPa1/2 [6]. Then, the
Methyl oleate [4] 16.4 solubility parameter calculation of the naphthenic oil is quite
Methyl oleate [6] 15.5 straightforward according to
Methyl linoleate (this work) 16.6
Methyl stearate (this work) 16.7 (0.45 × 16.8) + (0.35 × 12.8) + (0.2 × 18.5) = 15.7 MPa1/2 .
Methyl palmitate (this work) 16.6 (13)
Biodiesel (this work) 16.65 ± 0.05
Biodiesel [7] 17.56 ± 0.27 (c) Aromatic Oil. It is essentially made a “core” of two
condensed benzene rings (naphthalene) which are well repre-
sented indeed by naphthalene whose solubility parameter is
20.2 MPa1/2 [6], representing about 50% of the total carbon
Table 2: Solubility parameter of rubbers and mineral oils plasticiz- content. The naphthenic part of the oil can be represented by
ers.
the cyclohexane molecule which has a 𝛿𝑡 = 16.8 MPa1/2 [6],
𝛿𝑡 in MPa1/2 and the naphthenic molecules may represent 20% of the total
EPDM and butyl rubber [2] 16.1 carbon atoms. The paraffinic part of the molecule represents
16.5 about 30% of the total carbon atoms which may be best
Polyisoprene and natural rubber [2]
represented by neopentane which has a solubility parameter
Polybutadiene [2] 17.1
of 12.8 MPa1/2 [2]. Then, the solubility parameter calculation
Styrene-butadiene copolymer 20% styrene 17.4 of the aromatic oil is quite straightforward according to
(this work)
Styrene-butadiene copolymer 40% styrene 17.7 (0.5 × 20.2) + (0.2 × 16.8) + (0.3 × 12.8) = 17.3 MPa1/2 .
(this work)
(14)
Polystyrene [2] 18.7
Acrylonitrile-butadiene copolymer 20% 19.4
acrylonitrile (this work) 3.4. Evaluation of the Solubility of Rubbers in Selected Plasticiz-
ers. There are numerous ways of evaluation of the solubility
Acrylonitrile-butadiene copolymer 30% 20.6
acrylonitrile (this work)
of a given polymer P in a given solvent S; Van Krevelen [21]
suggests the criteria imposed by the following:
Polyacrylonitrile 28.7
Aromatic oil plasticizer [2] 16.4 2 2 2 0.5
Δ𝛿 = [(𝛿𝑑,𝑃 − 𝛿𝑑,𝑆 ) + (𝛿𝑝,𝑃 − 𝛿𝑝,𝑆 ) + (𝛿ℎ,𝑃 − 𝛿ℎ,𝑆 ) ] .
Paraffinic oil plasticizer [2] 15.3
17.3
(15)
Aromatic oil plasticizer (this work)
Naphthenic oil plasticizer (this work) 15.7 To predict solubility
Paraffinic oil plasticizer (this work) 14.2
Δ𝛿 ≤ 5. (16)

Alternatively, Hansen [6] has proposed a more sophisticated

atoms and which may be best represented by neopentane and relatively complex approach for the evaluation of the
which has a solubility parameter of 12.8 MPa1/2 [2]. The solubility of a polymer in a solvent. The problem in the
naphthenic part of the oil can be represented by the cyclo- present study regards the fact that, for all the solutes and
hexane molecule which has a 𝛿𝑡 = 16.8 MPa1/2 [6], and solvents considered here, we have available the total solubility
ISRN Polymer Science 5

parameter 𝛿𝑡 , but in most cases we do not have available the other rubbers reported in Table 3, but its compatibility
the separate contributions to 𝛿𝑡 in terms of 𝛿𝑑 , 𝛿𝑝 , and 𝛿ℎ . drops gradually from polyisoprene to polystyrene and nitrile
Therefore, we have preferred to adopt the simplest possible as intuitively expected. Naphthenic oil is instead a very good
approach in the evaluation of the solubility between a solvent for EPDM, butyl, and polyisoprene, but with BR and
polymer and a solvent which conform to the criteria imposed SBR, its compatibility gradually decreases. Aromatic oil is
by the following: instead very compatible with SBR and still acceptable also
for natural rubber and polyisoprene. Also, the last case is
|Δ𝛿| = (𝛿𝑡,𝑃 − 𝛿𝑡,𝑆 ) , (17) completely in line with the experience.
Less common plasticizers reported in Table 3 are the
a criteria proposed by Brydson [2]. adipate, sebacate, and phthalate esters. These esters (and other
Table 3 shows a summary of these calculations made similar) are used especially in the formulation of winter tire
according to (17). At the bottom of Table 3 are reported the treads. As expected the most aliphatic esters adipate and
|Δ𝛿| values of a series of methyl esters of fatty acids and sebacate have a wider compatibility with all rubbers while
a series of rubbers. From the data reported, it is evident the most aromatic esters based on phthalates appear more
that we must expect an excellent solubility of EPDM, butyl compatible with SBR, polystyrene, and nitrile rubber.
rubber, polyisoprene (natural rubber), polybutadiene, and In conclusion, the simplest approach of using the |Δ𝛿𝑡 |
SBR (styrene-butadiene copolymers) in all methyl esters of appears useful and completely in line with the experience.
fatty acids and consequently also in biodiesel which is just |Δ𝛿𝑡 | can be viewed as a quantitative estimation of a given
a mixture of different types of methyl esters of fatty acids. rubber solubility into a given plasticizer. In Table 3, we have
The reason of this expected solubility is derived from the used four color codes as a guidance of the solubility between
extremely low value in line with the disequation |Δ𝛿𝑡 | < the polymers in the plasticizer. The bold font indicates the
1. Indeed, our experiments on dissolution of polyisoprene, best solubility followed by the italic font and the bold italic
polybutadiene, and SBR-20 in biodiesel were completely font code. The underline font suggests already a certain lack
successful. Thus, the theoretical expectation of the solubility of compatibility to a certain extent.
of diene rubbers in biodiesel has found a clear experimental
confirmation. In this context, the solubility parameter of
3.5. Solubility Parameter and Behavior of a Plasticizer in
biodiesel 𝛿𝑡 = 17.6 MPa1/2 reported by other authors [7]
a Rubber Matrix. There is other useful information which
appears, after all, reasonably close to the value calculated
can be extracted from the solubility parameters and regard
by us for biodiesel 𝛿𝑡 = 16.6 MPa1/2 . In view of the the behavior of a plasticizer in a rubber matrix. In fact,
experimental results which have confirmed the easy solubility it is possible to distinguish between plasticizers which act
of diene rubbers in biodiesel, 16.6 MPa1/2 should be taken as internal lubricants from plasticizers which instead act as
as the reference value for the biodiesel solubility parameter. external lubricants. Internal lubricants are those plasticizer
Looking at Table 2, it is also possible to expect less solubility molecules which facilitate the movements of a polymer
by polystyrene and by nitrile rubber in biodiesel. A specific chain segment with regard to an adjacent polymer segment.
experiment of dissolution of polystyrene in biodiesel has External lubricants are instead low compatibility plasticizers
revealed that it is soluble, but the approximate concentration which tend to migrate on the surface of the rubber matrix
reached is 2 mg/mL, while in the case of polyisoprene, and they act as a processing aid, for example, in the extrusion
polybutadiene, and SBR, we were able to reach concentrations process or in conferring tackiness to the rubber surface.
as high as 10 mg/mL, and probably it was possible to go above Ideally, internal lubricants must have a high compatibility
that value without problems. with a rubber matrix, that is, |Δ𝛿𝑡 | → 0, and instead an
Table 3 shows also that the triglycerides of fatty acids have external lubricant is characterized by higher values of |Δ𝛿𝑡 |.
a solubility parameter very close to that of biodiesel and the Let us read the data in Table 3 under other optics: let us
methyl esters of fatty acids. This fact is not surprising; it is in change (17) into the following:
line with expectation, and hence, based on the data of Table 3,
it is possible to affirm that fatty acids esters either methyl Δ𝛿 = (𝛿𝑡,𝑃 − 𝛿𝑡,𝑆 ) . (18)
esters or under the form of glycerides are good plasticizers
of diene rubbers and in particular of EPDM, butyl rubber, In other words, let us now consider the sign of the interaction.
polyisoprene, polybutadiene, and SBR. A slight different The simplest case is that 𝛿𝑡,𝑃 ≈ 𝛿𝑡,𝑆 , and this condition
behavior in terms of solubility is expected for castor oil which corresponds again to the fact that the plasticizer and polymer
is characterized by a unique chemical structure among the are mutually soluble, and hence, the plasticizer acts also as an
fatty acids triglycerides, since it contains also hydroxyl groups internal lubricant.
due to ricinoleic acid. This fact explains the relatively high The condition when |Δ𝛿𝑡 | ≫ 0 means that we are dealing
solubility parameter of castor oil in comparison to the other with an external lubricant and can be resolved into two cases.
vegetable oils [3]. If 𝛿𝑡,𝑃 > 𝛿𝑡,S then Δ𝛿 > 0, and, of course, if 𝛿𝑡,𝑃 < 𝛿𝑡,𝑆 then
Table 3 shows also the solubility parameters and the |Δ𝛿𝑡 | Δ𝛿 < 0. In the first case, when the solubility parameter of
values with a series of rubbers of the conventional plasticizers the plasticizer is higher than that of the polymer, the sign
prepared from oil which were discussed in Section 3.3. Based is positive and the plasticizer acts as an external lubricant
on the |Δ𝛿𝑡 | values, paraffinic oil is suitable essentially for effective on the surface of the filler. The higher polarity and/or
EPDM and for butyl rubber. It is still acceptable also for aromaticity of the plasticizer implies that the plasticizer
6 ISRN Polymer Science

Table 3: Difference |Δ𝛿𝑡 | between the solubility parameter of the plasticizer and the solubility parameter of the rubber.

𝛿𝑡 in |Δ𝛿𝑡 | |Δ𝛿𝑡 | |Δ𝛿𝑡 | |Δ𝛿𝑡 | |Δ𝛿𝑡 | |Δ𝛿𝑡 | |Δ𝛿𝑡 | |Δ𝛿𝑡 |

MPa1/2 EPDM and IIR NR BR SBR-20 SBR-40 PS NITRILE-20 NITRILE-30
Paraffinic oil (this work) 14.2 −1.9 −2.3 −2.9 -3.2 −3.5 −4.5 −5.2 −6.4
Naphthenic oil (this work) 15.7 −0.4 −0.8 −1.4 −1.7 −2.0 −3.0 −3.7 −4.9
Aromatic oil (this work) 17.3 1.2 0.8 0.2 −0.1 −0.4 −1.4 −2.1 −3.3
Diisooctyl adipate [2] 17.8 1.7 1.3 0.7 0.4 0.1 −0.9 −1.6 −2.8
Dioctyl sebacate [2] 17.8 1.7 1.3 0.7 0.4 0.1 −0.9 −1.6 −2.8
Diethylhexyl phthalate [2] 18.2 2.1 1.7 1.1 0.8 0.5 −0.5 −1.2 −2.4
Dioctyl phthalate [6] 18.3 2.2 1.8 1.2 0.9 0.6 −0.4 −1.1 −2.3
Diethylhexyl phthalate [6] 19.0 2.9 2.5 1.9 1.6 1.3 0.3 −0.4 −1.6
Dibutyl phthalate [2] 19.2 3.1 2.7 2.1 1.8 1.5 0.5 −0.2 −1.4
Olive oil [3] 16.9 0.8 0.4 −0.2 −0.5 −0.8 −1.8 −2.5 −3.7
Soybean oil [3] 16.2 0.1 −0.3 −0.9 −1.2 −1.5 −2.5 −3.2 −4.4
Sunflower oil [3] 16.7 0.6 0.2 −0.4 −0.7 −1.0 −2.0 −2.7 −3.9
Peanut oil [3] 16.1 0.0 −0.4 −1.0 −1.3 −1.6 −2.6 −3.3 −4.5
Lineseed oil [3] 16.4 0.3 −0.1 −0.7 −1.0 −1.3 −2.3 −3.0 −4.2
Brassica oil [3] 16.9 0.8 0.4 −0.2 −0.5 −0.8 −1.8 −2.5 −3.7
Castor oil [3]∗ 18.3 2.2 1.8 1.2 0.9 0.6 −0.4 −1.1 −2.3
Methyl erucate (this work) 16.6 0.5 0.1 −0.5 −0.8 −1.1 −2.1 −2.8 −4.0
Methyl oleate (this work) 16.7 0.6 0.2 −0.4 −0.7 −1.0 −2.0 −2.7 −3.9
Methyl linoleate (this work) 16.6 0.5 0.1 −0.5 −0.8 −1.1 −2.1 −2.8 −4.0
Methyl stearate (this work) 16.7 0.6 0.2 −0.4 −0.7 −1.0 −2.0 −2.7 −3.9
Methyl palmitate (this work) 16.6 0.5 0.1 −0.5 −0.8 −1.1 −2.1 −2.8 −4.0
Biodiesel (this work) 16.6 0.5 0.1 −0.5 −0.8 −1.1 −2.1 −2.8 −4.0
Biodiesel [7] 17.6 1.5 1.1 0.5 0.2 −0.1 −1.1 −1.8 −3.0
∗
Hansen reports a value of 20.4 MPa1/2 .
EPDM: ethylene/propylene/diene rubber; IIR: butyl rubber; NR: natural rubber (polyisoprene); BR: polybutadiene; SBR-20: styrene/butadiene copolymer 20%
styrene; SBR-40: styrene/butadiene copolymer 40% styrene; PS: polystyrene; NITRILE-20: acrylonitrile/butadiene copolymer 20% acrylonitrile; NITRILE-30:
acrylonitrile/butadiene copolymer 30% acrylonitrile.
Bold font : |Δ𝛿𝑡 | < 1.
Italic font : 1.0 < |Δ𝛿𝑡 | < 1.9.
Bold italic font : 1.9 < |Δ𝛿𝑡 | < 2.9.
Underline font : |Δ𝛿𝑡 | > 3.

becomes preferentially adsorbed on the filler surface to which the plasticizer is possible especially if the polymer matrix
it has higher affinity forming a layer between polymer and is highly polar in comparison to the modest polarity of the
filler enhancing the processability which can be viewed in plasticizer. Plasticizer bleeding is a risk is designed with a
terms of a facilitation of filler incorporation and dispersion large amount of plasticizer.
inside the polymer matrix. The plasticizer by forming a
film on the surface of the filler reduces the surface energy 3.6. Biodiesel Behavior in a Rubber Compound. Based on
of the filler itself and consequently facilitates the polymer- the data of Table 3, biodiesel acts as an internal lubricant
filler interaction [6]. The estimated solubility parameters with apolar rubbers like EPDM, butyl rubber, polyisoprene,
of some fillers are worth mentioning here: carbon black polybutadiene, and SBR at moderate amount of styrene. In
𝛿𝑡 = 22–33 MPa1/2 and silicate fillers 𝛿𝑡 = 30–40 MPa1/2 . the case of high styrene SBR (>40%), the biodiesel starts to
Furthermore in the condition of 𝛿𝑡,𝑃 > 𝛿𝑡,𝑆 , then Δ𝛿 > 0; the work also as an external lubricant, and being Δ𝛿 < 0, it is
plasticizer may act as a tackifier on the surface of the rubber evident that in this case the biodiesel will concentrate on the
compound but the tackifier behavior is also affected by other external surface of the rubber compound.
properties of the plasticizer like its softening or melting point There are little differences in the plasticizing effects
and the working temperature range where one is operating. of biodiesel in comparison for instance with an aromatic
The opposite conditions 𝛿𝑡,𝑃 < 𝛿𝑡,𝑆 then Δ𝛿 < 0 imply mineral oil. The latter shows also high compatibility with all
instead that the polymer is more polar or aromatic than the the common rubber shown in Table 3 with some exception
plasticizer; these are considered the most desirable conditions with EPDM and butyl rubber. Thus, also an aromatic mineral
to have a plasticizer which acts as a simple external lubricant oil (like for instance a T-RAE = Treated Residual Aromatic
of the rubber compound as a flow improver, for example, Extract) acts as an internal lubricant with polyisoprene,
in the extrusion process. Also in this case, the exudation of polybutadiene, and SBR, and only with polystyrene and
ISRN Polymer Science 7

Table 4: Cure kinetics and scorch. Table 5: Cured physical properties.

∘
Rheometer test at 160 C Reference Biodiesel Reference Biodiesel
ML (dNm) 3.07 3.13 Tensile strength (MPa) 18.7 16.9
MH (dNm) 15.04 13.24 Modulus at 50% (MPa) 1.06 0.88
MH-ML (dNm) 12.0 10.1 Modulus at 100% (MPa) 1.69 1.29
T10 (min) 3.34 3.25 Modulus at 200% (MPa) 4.29 2.90
T50 (min) 5.07 4.50 Modulus at 300% (MPa) 8.26 5.61
T90 (min) 8.19 7.34 Modulus at 400% (MPa) 12.28 8.70
Mooney scorch (min) 127∘ C 19.00 17.26 Modulus at 500% (MPa) 16.03 11.73
Mooney viscosity 100∘ C 52 49 Elongation at break % 580 687
Hardness shore A 69 64
Hardness shore A at 100∘ C 57 54
nitrile rubber, it starts to work as an external lubricant with
possible blooming on the surfaces of these polymer matrices.
Conversely, the aromatic mineral oil could partly act as an
observe a reduced Mooney viscosity (3 Mooney points lower)
activator of filler surface when used with EPDM and butyl
of the compound prepared with biodiesel in comparison to
rubber.
the reference rubber compound with mineral oil. This effect
on viscosity can be simply explained by the fact that the
3.7. Experimental Behavior of Biodiesel in a Passenger Tread viscosity of pure biodiesel is considerably lower than that of
Compound in Comparison to a Mineral Aromatic Oil. Rubber an aromatic oil plasticizer of the type of T-RAE. The lower
compounds with SBR are commonly compounded with viscosity of biodiesel is also manifested in the relative rubber
aromatic mineral oil of the type of T-RAE. In this study compound. In general, a lower viscosity is judged positively
we have replaced the free mineral oil of a standard rubber because it improves the rubber compound processability, for
compound intended for tread application with a commercial example, it gives a better extrudability.
biodiesel. As reported in the experimental section, in an SBR- In Table 5, the physical properties of the cured rubber
based rubber compound 20 phr of free oil was substituted compounds are reported. As already anticipated from the
with 20 phr of biodiesel. Table 4 shows the results of such a rheometrical properties and from the lower crosslinking den-
change in terms of rheometrical properties (a measurement sity of the compound plasticized with biodiesel, in Table 5,
of the cure kinetics and crosslinking density made at 160∘ C), A lower tensile strength and systematically lower modulus
Mooney scorch time (a measurement of the tendency to pre- for such a compound in comparison to the reference can be
mature vulcanization made at 127∘ C), and Mooney viscosity observed. The reduction of tensile strength in the biodiesel-
(a measurement of the viscosity of the compounds expressed based compound is about −10% in comparison to reference,
in Mooney scale and made at 100∘ C). and it is compensated by a higher elongation at break (+18%)
The rheometrical data show that biodiesel reduces the for the biodiesel-based compound which is again due to the
maximum torque (MH), and consequently, it reduces also lower crosslinking density of this compound. The modulus
the crosslinking density of the compound as shown by the measured at lower and high extension in the biodiesel-
lower value (12% less) of the MH-ML in comparison to based compound is systematically lower than the reference
that of the reference compound. This result is derived from compound, and the effect is more pronounced at higher
the fact that biodiesel is a reactive plasticizer sensitive to elongations. As expected also the hardness of the biodiesel-
the sulphur-based vulcanization because the methyl esters based compound is lower than the reference. After all, the
of fatty acids composing the biodiesel are unsaturated. For hardness is a measure of modulus under compression rather
example, biodiesel produced from rapeseed oil has an iodine than extension and at low displacements, and in fact, the
number (a measurement of the unsaturation) of 110 g/100 g differences in comparison to the reference are limited to −6%
and reaches the value of 130–135 g/100 g when the biodiesel or −7%.
is derived from soybean and sunflower. The biodiesel used The viscoelastic properties of a cured rubber compound
by us was of rapeseed origins. The mechanism which leads are measured at the mechanical spectrometer. Two compo-
to a reduction of the crosslinking density implies that part nents are the key parameter of the viscoelastic behavior: the
of the available sulphur is lost in crosslinks between the elastic modulus G󸀠 which is known also as storage modulus
󸀠󸀠
plasticizer and the rubber chains and between plasticizer and the viscous modulus 𝐺 which is known also as loss
molecules, while in the reference compound all the available modulus [21]. The two parameters were measured in our case
sulphur is used in the crosslinking reactions between the at 1% extension and at a frequency of 80 Hz. The ratio between
polymer chains, being sulphur not reactive with aromatic the viscous modulus and the elastic modulus is known as
oil. Another aspect which can be observed from the data tan𝛿:
in Table 4 regards the fact that biodiesel accelerates cure
kinetics in comparison to reference, and this fact is observed 󸀠󸀠

also in a reduced Mooney scorch time in comparison to 𝐺

tan 𝛿 = 󸀠 . (19)
reference compound. Furthermore, in Table 4, it is possible to 𝐺
8 ISRN Polymer Science

Table 6: Dynamic properties at the mechanical spectrometer. lower tensile, and higher elongation. The low modulus is
beneficial for the low temperature behavior of the biodiesel-
Reference Biodiesel based rubber compound which shows potential application
󸀠 ∘
Elastic modulus 𝐺 at −20 C 206.3 105.0 in winter (snow and ice) passenger tire tread formulations
Tan𝛿 0.438 0.231 without detrimental effects in the dry traction and rolling
Elastic modulus 𝐺󸀠 at 0∘ C 81.3 55.8 resistance. Some potential weakness of the biodiesel-based
Tan𝛿 0.190 0.165 rubber compound could occur in the wet traction. However,
Elastic modulus 𝐺󸀠 at +30∘ C 36.5 27.9 the present study is only an exploratory study aimed to
Tan𝛿 0.177 0.165 demonstrate the potentiality of biodiesel as an alternative
Elastic modulus 𝐺󸀠 at +70∘ C 22.4 17.3
plasticizer from renewable sources against the mineral oil
derived plasticizers. Further work is certainly needed to
Tan𝛿 0.169 0.166
optimize the behavior of the biodiesel. For example, it should
be part of the fine tuning work the necessity to increase
󸀠
the modulus of the biodiesel-based rubber compound and
In Table 6, the 𝐺 and tan𝛿 values measured on the refer- this can be achieved by increasing the sulphur content of
ence and on the biodiesel-based compound under different the formulation. It is expected that a correct increase in the
temperature conditions are reported. It is evident that the sulphur content will be beneficial in increasing the moduli
dynamic behavior of the two compounds is quite different. and the tensile to the same level of the reference compound,
As usual, the biodiesel-based compound is affected by a low but the interesting potential application in winter tire tread
󸀠
𝐺 which is a consequence of the general lower crosslinking will remain evident even after the fine tuning adjustments.
󸀠
density. However, low 𝐺 at low and very low temperatures
is judged positively for a winter tread because the low values References
of the elastic modulus imply more grip even under extreme
conditions of traction on snow or ice [23, 24]. Conversely, the [1] W. A. Schneider, F. Huybrechts, and K. H. Nordsiek, “Process
󸀠 oils in oil extended SBR,” Katschuk Und Gummi Kuststoffe, vol.
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[23, 24]. Concerning wet traction, a predictor is the tan𝛿 experimental results,” in Medicinal Chemistry and Pharmaco-
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based compound gives a different behavior in a cured rubber biofuels,” In Vitro Cellular and Developmental Biology—Plant,
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