EUROPEAN

POLYMER
European Polymer Journal 43 (2007) 4143–4150
JOURNAL
www.elsevier.com/locate/europolj

Macromolecular Nanotechnology

Rubber network in elastomer nanocomposites
M.A. Lo´pez-Manchado *, J.L. Valentı´n, J. Carretero, F. Barroso, M. Arroyo
Institute of Polymer Science and Technology, CSIC, Juan de la Cierva, 3, 28006 Madrid, Spain

Received 17 April 2007; received in revised form 28 June 2007; accepted 8 July 2007
Available online 24 July 2007

MACROMOLECULAR NANOTECHNOLOGY
Abstract

The influence of inorganic nanoparticles on crosslinking mechanism of elastomers has been evaluated by applying the
tube model on equilibrium statistical mechanics. The results have shown that a highly ordered structure with a huge
amount of entanglements, wherein the polymer is nanoscopically confined, is formed by the addition of nanoparticles.
These physical links exhibit freedom of movement under stretching, but in a lower volume because of confinement. That
is, network molecular parameters such as lateral tube dimensions or average molecular mass of the chains decreased in
presence of nanoparticles. 
2007 Elsevier Ltd. All rights reserved.

Keywords: Nanocomposites; Rubber networks; Crosslinks; Inorganic nanoparticles; Natural rubber

1. Introduction understanding of the nanofiller/polymer interaction
mechanism, still exists today. In the particular case
In recent years, hybrid organic–inorganic nano- of elastomer matrices, a deeper knowledge of the
composites, consisting of a polymeric matrix and a influence of nanoparticles on the rubber network
layered silicate has inspired scientists in a range of is of crucial importance to explain the improved
potential applications. Due to their nanometer properties of these nanocomposites.
phase dimensions, polymer nanocomposites (PNCs) The statistical mechanics of elastomers, i.e. cross-
exhibit unique properties even by the addition of linked long polymers chains, is one of the most chal-
just a low weight percentage (<5 wt%), not shared lenging problems in polymer physics [5–8]. Rubber
by their microcounterparts or conventional filled elasticity is a unique phenomenon which has
polymers [1–4]. Hence, several polymers have been attracted the attention of many researchers. It has
used for preparing nanocomposites. Most of these been shown that the theory of networks is a typical
works are focused on synthesis, characterization example of a strong link between modern condensed
and properties of nanocomposites, but, a poor matter physics and applied materials science [9].
Most of the classic theories on elastomers [10,11]
*
and rubber elasticity have been developed based
Corresponding author. Tel.: +34 91 5622900; fax: +34 91
5644853.
on the free energy to predict reasonably the stress–
E-mail address: lmanchado@ictp.csic.es (M.A. Lo´pez-Man- strain relation. These theories are based on oversim-
chado). plified assumptions, i.e., ideal chains where the

0014-3057/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2007.07.023

a load cell of 50 N was used. 4301 model. In order to minimize dynamical contri- butions. Of course.A. Fur. The recipes of the com- figurations parallel and perpendicular to the axis of pounds are compiled in Table 1. tensile tests were carried out at a cross-head 2. N234 a Among several versions of the entanglement Benzothiazyl disulfide. In 3. To obtain a good sensitivity. / European Polymer Journal 43 (2007) 4143–4150 crosslinks did not really move at all.5 mm/min up to break (strain rate de/ dt  2.5 2. tion of 125 cm3/100 g. ISAF carbon black kindly supplied by Cabot. Carbon black. Lo´pez-Manchado et al. saponite with cation exchange capacity (CEC) value of 70 meq/100 g was provided by Tolsa (Spain). the curing curves of the MDR 2000E. Therefore.03). This will allow to clarify previous works [16. These models rely on strong Nanoparticle – 5 – homogeneous networks. it allows a proper ascription of crosslinks vulcanized at 150 C in a thermofluid heated press. Natural rubber 100 100 100 ories are not realistic due to not only the idealiza.5 the molecular forces and chain entanglements are MBTSa 1 1 1 neglected. ingredients except sulphur were added to the elasto- mined volume with tube-like geometry. Lateral fluc. finally.4. b model on equilibrium statistical mechanics.14]. As can ratories following a previously described procedure be observed the organoclay exhibits a stronger rein- [15]. Details on the characterization of organoclay/ mechanism by applying the tube model theory in elastomer nanocomposites by X-ray diffraction and order to explain the improved properties of these transmission electron microscopy can be found in elastomer nanocomposites. 4144 M.5 2. Vulcanizing condi- the tube. the mechanism of reinforcement by highly aniso. where fluctuations in cross. Within this mer previously to the incorporation of the filler and. and constraints contribution to the mechanical The vulcanization time of the compounds corre- behaviour and a reliable determination of crosslink sponds to the optimum cure time (t95) derived from densities [13. these classical the. the Phenyl beta napthyl amine. most empirically useful and successful seems to be the tube model [12]. This model takes into account tion of 120 m2/g and dibutylphtalate (DBP) adsorp- MACROMOLECULAR NANOTECHNOLOGY the importance of topological constraints or entan. Results and discussion order to increase the interlayer spacing.17]. Uniaxial stress–strain measurements were per- tropic fillers which at present time is not yet fully formed at 25 ± 1 C on an Instron dynamometer understood. was also used in this work.78 · 104 s1). Specimens Therefore. in an open two-roll mill.001–0. Na+-activated deviation 0. Rheometer MDR 2000E. but also are strongly limited by networks PBNb 1 1 1 interconnectivity. at room tem- tuations of a polymer strand are limited by the perature. 1. each ated at a speed ratio of 1:1. the clay has been organically modified by cation exchange The stress–strain curves of the studied materials reaction with octadecylammonium salt in our labo. Natural rubber was kindly supplied by Malay. glements along the contour of strands. and thus the Table 1 problem reduces to that of a single chain between Recipes of the rubber compounds two fixed links that deform simultaneously when NR NR/nanoparticle NR/carbon black the solid is deformed. Zinc oxide 5 5 5 tion of real chains to simple random paths where Stearic acid 1 1 1 Sulphur 2. The rotors oper- presence of neighbouring chains. the aim of this work is to analyze the were mechanically cut out from the vulcanized pla- influence of nanoparticles on elastomer crosslinked ques. sulphur was added. The results were the sian Rubber under the trade name CV 60 (Mooney average of at least three measurements (standard viscosity. – – 5 link densities are not allowed. in uniaxial extension are shown in Fig. ML (1 + 4) 100 C 60). Rubber compounds were prepared. The vulcanization individual chain is effectively confined in a deter. tube. compounds as reported in the literature [16]. forcing effect than carbon black on natural rubber under the trade name N234 with nitrogen adsorp. The tube model is particularly successful tions (temperature and time) were previously to explain the uniaxial stress–strain measurements determined by means of a Monsanto Moving Die of both unfilled and filled polymer networks. Experimental section speed of 0. Rubber compounds were thermore. In . the polymer is free to explore all possible con.

This state. r rM ¼ ¼ Gc þ Ge f ðkÞ ð1Þ defined as the length/width ratio of the particle ðk  k2 Þ was introduced. it can be seen that at low deforma- 2 kb=2  kb tions. the constitutive equa. logical constraints or entanglements). (1)–(4) when plotting the nal length of the sample in the direction of the reduced stress rM against deformation function. In the case of filled rubbers and in order to con- sider the likely contributions of matrix overstrain due to the presence of filler particles. and Ge and butions of chemical crosslinks. Based on this model.23] G MACROMOLECULAR NANOTECHNOLOGY Fig. tropic character is important. 1. k is the macro. a curve is obtained. a large and for almost complete converted dry networks made rather abrupt upturns in the reduced stress since from long primary highly crosslinked chains so that the entanglements behave as effective crosslinks. the fil. k 0 which is given by the following expression: [19–21] k0 ¼ ðk  1Þveff þ 1 ð3Þ where the effective amplification factor. for non-spherical particles. Thus. For the studied mate- mation function which is given by the following rials these values are reported in Table 2. The parameter b was introduced to take into effect is more evident in the case of the nanoparti- account the strong swelling dependence of con. [18] when analyz- ing NR compounds. this statement has been experimentally corroborated by Marzocca et al. ical rigid particles [24]. the entanglements formed tube in the stretched state and an slippage takes place. respectively. tion of the filler. be taken into account to predict the modulus of a tend a sample of rubber of a determined clay reinforced nanocomposite. according to Eqs.. the deforma- tion k. Obviously. a shape factor f. From Fig. cles.e. the molecular mass of a strand is much smaller than This increase in reduced stress is critical to explain . This equation is based on the Einstein’s network were analyzed by applying the tube model equation for the viscosity of a suspension of spher- theory. At higher elongations. that at the inter- is the elastic modulus that corresponds to the contri. with an effective undeformed cross-sectional area. In general. is ex- pressed as [22. As the net- ter which describes the relation between the de. volume fraction larger than the theoretical one [25]. losing effectiveness which leads undeformed tube corresponding to the equilibrium to a considerable decrease in reduced stress.A. mediate regions shows a straight line. Ge is related to the Gc can be calculated from its slope and y-axis inter- topological tube-like constraints and f(k) is a defor. and then. and G0 is the modulus of the ma- ence of these fillers on the crosslinked rubbery trix. must be replaced by an intrinsic strain ratio. veff ¼ 1 þ 2:5f ueff þ 14:1f u2eff ¼ ð4Þ G0 order to understand this different behaviour. relevant discussed later. b is taken as 1. scopic extension ratio defined as the ratio of the fi. which is reflected in a higher slope. Since in layered silicates the aniso- where rM is the reduced stress. a shape factor has to nal stress defined as the tensile force required to ex. cept at f(k 0 ) = 0. Lo´pez-Manchado et al.17]. r denotes the nomi. Stress–strain curves of the studied materials. where ueff corresponds to the effective volume frac- ler/polymer interaction mechanism and the influ. veff. work chains are stretching. expression: in the case of the unfilled rubber sample f(k 0 ) = f(k). corresponding to the rubber matrix. 2). the elastic response of the material is given by f ðkÞ ¼ f ðk ¼ 1Þ ¼ 1 ð2Þ b k2  k1 both contributions (chemical crosslinks and topo- where b can be considered as an empirical parame. / European Polymer Journal 43 (2007) 4143–4150 4145 the molecular mass of the primary chains [13. Gc f(k 0 ) (Fig. stretch to the initial length before deformation. In addition. Guth and Gold generalized tion of a uniaxial deformation of an incompressible the Einstein concept by adding the quadratic term sample comes from two contributions: to account for interaction between particles. as will be straints. M. i. 2.

Its molecular of crosslinks occurs).126 4404 2.92 g/cm3 for natural orientation level of polymer chains by birefringence rubber) and NA is the Avogadro number. crystallization of elastomer under stretching by In addition. Lo´pez-Manchado et al.304 0. both contributions are increased in pres- ence of nanoparticles (Table 2). The authors reported that the decrease increase in the stress at high strains. / European Polymer Journal 43 (2007) 4143–4150 ical crosslinks and physics entanglements that do not lose their efficiency with the deformation. It is worthy network chains is connected to tc according to the to note that this rapid increase in the stress is more relation: noticeable in presence of the organoclay. and therefore act as crosslinks. Reduced stress versus deformation at room temperature. of polymer-filler couples and short bridging chains particles) increase the Gc contribution due to the between the filler particles which enlarge the exten- formation of a higher number of interactions. So.460 0. so. fine the diffusion of a polymer chain within a tortu- Table 2 Network molecular parameters Gc (MPa) Ge (MPa) tc (nm3) Mc (g/mol) d0 (nm) Rc (nm) ne NR 0. 4146 M. These results are in concor- small amounts of organoclay due to strong interac. when the nanoparticles are used as ber under uniaxial extension by the addition of nanoreinforcements.A. which explains the abrupt network [13]. in par- increase in the crystallization process of natural rub. in Mc is equivalent to an increase in the formation Both fillers (carbon black and organoclay nano.23 7. ticular. authors when analyzing the influence of carbon tallites thus so formed act as additional crosslinks black on the average molecular mass of elastomer in the network structure.259 0.10 6. Mc sensi- and infrared dichroism.00 3. By applying the tube model theory. where the contribution corresponding to topological constraints or entanglements is decreased.31] have shown that this ence of organoclay nanoparticles due to a deep inter- increase in modulus is associated to the induced action filler/matrix at the interface. It is deduced that the effec- versy.26–29] have attributed tive network density is increased by the addition of it to the finite extensibility of the network chains both fillers. T is the temperature. 2. both moduli.253 2189 1. are not changed under deformation. Further crys. Similar M c ¼ qP N A =mc ð6Þ conclusions have been reported by Joly et al.521 0. Gc is associated to the effec- tive crosslinks density by the following expression: G c ¼ Ac t c K B T ð5Þ where tc is the network chain density. This means The entanglements or physical constraints con- that it is no possible to differentiate between chem. KB is the Boltzmann constant origin has been the source of considerable contro.148 3751 2. The authors verified an bly decreases by the addition of both fillers.5 is assumed since Gc is calcu- lated to infinite deformation where free fluctuation the ultimate properties of the material.53 6. Ac is a micro- MACROMOLECULAR NANOTECHNOLOGY Fig.52 . the average molecular mass of the molecular orientation at high strains. and others [30. that sion of the filled network.27 NR/nanoparticle 0. However.55 8. several authors [10. and.251 0.65 5. Gc and Ge are related to the molecular network parameters (Table 2). [25] when analyzing the effect of an organoclay on the where qP is polymer density (0. it is notewor- thy that in spite of conventional fillers like carbon black. this effect being more evident in the pres- segments.42 NR/carbon black 0.196 0. dance with the observations carried out by other tions between the polymer and filler. structure factor that considers the fluctuation of the crosslinks (a value of 0.

So. (<5 wt%) is enough to interact with the total rubber The tube radius is also related with the mean mass. natural rubber calculated through Ms = qNA/ns is the mobility of the rubber chains is higher (Fig. 1=2 B S d 4ð6Þ 0 but also because limits the movement of rubber where nS is the polymer segment number density. used. which is related to the rubber. i. gled structure due to the formation of intense tion mechanism for both fillers is evidenced. by the presence of neighbouring d 0 ¼ ls n1=2 e ð10Þ chains.e. Rc. G0N ¼ 0:46 MPa was compound.A. So. However. with a loss . Nevertheless. This tuation range of a chain segment. culated by the expression: On the other hand. at low filler loads in the stant in the system under study. The rubber is nanoscop- compounds are summarized in Table 2. carbon black covers only a little rubber taken from the literature [33. as number of statistical segments between successive corroborated from molecular network parameters. However. According ically confined forming a highly ordered and entan- to these results.. lS chains. change in a significant way (Table 2). Thereby. Ge is rubber phases. nS is a parameter explains why the rubber samples loaded with high that can be obtained through the next equation: carbon black contents show an increase in strength !1=2 at different strains but to the detriment of the elastic   MACROMOLECULAR NANOTECHNOLOGY 9:5 G0N characteristics of the rubber compound.14. the inorganic nanoparticles are char- als ls < d0 < Rc which is in concordance with the re. which is reflected in ment (0. On the basis of this model. materials even at low filler percentages in the com- The effect of carbon black on filled rubber prop. / European Polymer Journal 43 (2007) 4143–4150 4147 ous path acting as a transient crosslink. through the expression: the addition of nanoparticles decreases the tube dimensions. new materials. and then.34]. due to its inorganic nature  1=2 the nanoparticles mainly exhibit physical absorp- Mc Rc ¼ lS ð9Þ tions with the elastomer matrix. which restricts the movement of the rubber All network molecular parameters of the studied chains to a lower volume. in a particular Ms interphase. a few rubber chains remain free. rubber is likely to adhere on several carbon black tional tubes within the bulk rubber by the following surface sites. It can be observed that for the studied materi. tive cross-link density tc. The constraint modulus. 3a). Lo´pez-Manchado et al. so the optimum sults reported by other authors on their studies on dispersion of even a small quantity of nanoparticles several elastomers [13. it is worthy to note that the erties can be successfully described through the chains freely move in uniaxial extension since the entanglement-bound rubber model (EBRM) [36]. acterized by a high aspect ratio. the entanglements slippage in the is the average length of the Kuhn’s statistical seg. i.7 g/mol for the molecular mass of weaker than in carbon black compound. Therefore.35]. 3. in an exfoliated nanocomposite. is responsible of the high performance of these sented in Fig. which is controlled by In other words. 3b. mer interface. the bound rubber is essentially immo- expression: [13] bile in this model. pound. restricting transition zone between the highly immobilized the slippage of the chains during deformation under and localized bound rubber and the mobile bulk an applied stress [32].88 nm for natural rubber) and d0 is the fluc. entanglements.e.85 nm3 is obtained for the nS con. a sensible decrease of Ge value (Fig. a huge amount of rubber is still free The root-mean-square end-to-end distance of the as reflected in Fig. Because. bound rubber is also reduced. the interaction with the rubber is where Ms = 67. So. M. the entangled bulk rubber with bound rubber in a the polymer is nanoscopically confined. This structure mechanism of reinforcement is schematically repre. This strong transition layer pro-  2 duces an increase of Gc value. the average molecular parameters do not average molecular mass of these chains was also cal. the carbon black affects which explains the good elastic properties of these the rubber property through its effect on the effec. a different filler/elastomer interac. it nS ¼ ð8Þ is important to note that the reinforcement of car- b l3s K B T bon black is restricted in a zone at the filler/elasto- where a value of 3. a single molecule of bound related to the lateral dimensions of the configura. 3c). ne. A likely nanoparticle/elastomer interactions. not only because 1 lS Ge ¼ K Tn ð7Þ the formation of strong filler–rubber interaction. percentage. slippage of the entanglements is not hindered. in relation to the unfilled mobile network chains.

This topological interactions among entangled mole- explains the improved properties of these innovative cules.V ¼ oL T. an increase fact is corroborated since the Ge/Gc ratio slightly of f obtained from mechanical measurements is varies for nanoparticles in relation to pristine natu- associated with a loss in chain entropy.A. is observed. / European Polymer Journal 43 (2007) 4143–4150 MACROMOLECULAR NANOTECHNOLOGY Fig.V . 3d). the mobility of rubber chains is limited in its lateral nent and then: f ¼ T oS oL T. S is the entropy. in all networks theories based on nanoparticles improves the strength and toughness topological invariants. but also from ison with that of bulk rubber (Fig. whereas a clear decrease in the case of reflects a more ordered system due to the confine. 4148 M. Schematic representation of filler/polymer interaction. This T the absolute temperature. Nevertheless. L the length of the sample and hardly hindered decreasing under stretching. where F is fluctuations by the presence of neighbouring chains. Therefore. This results in the formation of a assumed that the elastic retractive force of a rub. as expected in the presence of nanoparticles. highly ordered and entangled structure. These results are supported from a cles do not exhibit an optimum compatibility with thermodynamic point of view. This statement is of cru- ment. cial importance to understand how the addition of In addition. in deformed elastically active chains. these nanoparti- materials [16. 3.17]. wherein ber-like material depends on theoFentropy  compo. it has been assumed that of the material without sacrificing the elastic proper- the retractive force exhibited by polymeric networks ties of the rubber compound. V the vol. the slippage of the physical joints is ume of the system. in chain entropy associated to the reduction in the comes not only from the entropic forces generated number of possible chain configurations in compar. carbon black. Since the internal organic polymers. mainly to physical energy term can be considered negligible it is adsorptions. Lo´pez-Manchado et al. giving rise. which ral rubber. Helmholtz free energy. . Due to its inorganic nature.

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