Cellulose (2013) 20:417427 DOI 10.

1007/s10570-012-9830-1

ORIGINAL PAPER

Physicomechanical properties of nanocomposites based on cellulose nanobre and natural rubber latex
Eldho Abraham B. Deepa L. A. Pothan Maya John S. S. Narine S. Thomas R. Anandjiwala

Received: 5 July 2012 / Accepted: 12 November 2012 / Published online: 22 November 2012 Springer Science+Business Media Dordrecht 2012

Abstract Cellulose nanobres (CNF) with diameter 1060 nm were isolated from raw banana bres by steam explosion process. These CNF were used as reinforcing elements in natural rubber (NR) latex along with cross linking agents to prepare nanocomposite lms. The effect of CNF loading on the mechanical and dynamic mechanical (DMA) properties of NR/CNF nanocomposite was studied. The morphological, crystallographic and spectroscopic changes were also analyzed. Signicant improvement of Youngs modulus and tensile strength was observed as a result of addition of CNF to the rubber matrix especially at higher CNF loading. DMA showed a change in the storage modulus of the rubber matrix upon addition of CNF which proves the reinforcing
E. Abraham S. S. Narine Trent Biomaterials Research Program, Trent University, Peterborough, ON, Canada E. Abraham B. Deepa L. A. Pothan (&) Department of Chemistry, Bishop Moore College, Mavelikkara 690 101, Kerala, India e-mail: lapothan@gmail.com E. Abraham (&) S. Thomas School of Chemical Sciences, Mahatma Gandhi University, Kottayam 686 560, Kerala, India e-mail: eldhoabraham@gmail.com M. John R. Anandjiwala Polymers and Composites Competence Area, CSIR, Materials Science and Manufacturing, Port Elizabeth, South Africa

effect of CNF in the NR latex. A mechanism is suggested for the introduction of the Zncellulose complex and its three dimensional network as a result of the reaction between the cellulose and the Zinc metal which is originated during the composite formation. Keywords Bionanocomposites Fibre/matrix bond Thermomechanical properties Natural rubber Nanocellulose Zncellulose complex

Introduction There is currently a considerable interest in processing polymeric composite materials lled with rigid particles having at least one dimension in the nanometer range. Because of the nanometric size effect, these composites display some unique properties with respect to their conventional microcomposite counterparts (Dufresne et al. 1996). In the context of both biomass valorization and nanocomposite materials development, cellulose nanobres used as a ller in a polymeric matrix appear to be an interesting reinforcing agent (Angles and Dufresne 2000; Angellier et al. 2005). Cellulose is the most abundant and renewable biomaterial on earth and is totally biodegradable. Furthermore, compared to platelets like morphology of nanocrystals extracted from other sources like starch and potato, CNFs present the originality to have a rod like morphology having very high aspect ratio

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which gives exceptional characteristics to the nanobres (Putaux et al. 2003; Youssef et al. 2010). We have prepared CNFs by a patented steam explosion technique in order to extend their use in nanocomposite applications (Abraham et al. 2011). The preparation of CNF by this technique will give additional advantages over earlier ones by the high yield (*60 %) and the isolation of the nanobre as embedded in the raw bre entity. They consist of crystalline nanobres about 1040 nm diameter with a length of few micrometers. Cellulose nanobres have a density of 1.5 g/cm3 and it has high value of tensile strength (*10 GPa) and Youngs modulus (*134 GPa) (Schurz 1999). In the past decades, research has been focused on the development of other reinforcing agents to replace carbon black in rubber compounds since it is potentially toxic and it gives to the rubber a black color. Recently kaolin and silica were commonly used as reinforcing agents, but their reinforcing properties are lower than those obtained with carbon black. A variety of clays (Kim et al. 2004) have been used to obtain unusual nanocomposites by exploiting the ability of the clay silicate layers to disperse into polymer matrices. The use of clay minerals such as montmorillonite (Vu et al. 2001) and organoclays (Bala et al. 2004) has been extended to natural rubber, and they seem to be a potential substitute to carbon black. When compared with glass bers, silica and carbon black, CNF as reinforcing ller in composites has many advantages: low cost, low density, easy processability, and little abrasion to equipment, renewability, and biodegradability. Nanocomposites of natural rubber lled with cellulose bre were reported by earlier researchers (Bendahou et al. 2010; Siqueira et al. 2011; Visakh et al. 2012). But we have specically used CNF which is obtained by steam pre-treatment of the banana bast
Table 1 Formulation of the cross linked NR/CNF composite

bre as the reinforcing ller for NR latex. More over the crosslinking agents like Zinc dithiocarbomate (ZDC), Zinc mercapto benzothiozole (ZMBT), Zinc oxide (ZnO) and sulfur were used during the processing stage to get a product with maximum mechanical and barrier properties.

Materials Natural rubber latex, the matrix Centrifuged latex of natural rubber was kindly supplied by Rubber Board, Kottayam, Kerala, India. It contained spherical particles with an average diameter around 1 lm, with a dry rubber content of 60 DRC and it contains more than 98 % of cis-1,4polyisoprene. Cellulose nanobre, the reinforcement A homogenous CNF (with a diameter of 1060 nm) dispersion which is obtained by the steam explosion of the banana bre is used as the reinforcing material. As reported in our previous work, the isolation of the nanobe includes the alkali treatment coupled with steam explosion, bleaching and mild acid hydrolysis with oxalic acid are the main preparation steps (Abraham et al. 2011). Film processing The CNF is mixed with the NR matrix along with other cross linking components as described in the Table 1 formulation. The composite lms were prepared from prevulcanised latex (Stephen et al. 2006) by casting on

Weight % in the nanocomposite Neat NR Centrifuged natural rubber latex Potassium hydroxide solution Sulphur dispersion ZDC dispersion ZMBT dispersion Zinc oxide dispersion CNF dispersion 96.5 0.35 1.5 0.75 0.6 0.3 0 2.5 % 94 0.35 1.5 0.75 0.6 0.3 2.5 5% 91.5 0.35 1.5 0.75 0.6 0.3 5 7.5 % 89 0.35 1.5 0.75 0.6 0.3 7.5 10 % 86.5 0.35 1.5 0.75 0.6 0.3 10

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a glass plate followed by drying. The prevulcanization of the compounded latex was conducted at 70 C for 2 h using water bath with constant gentle stirring. The sample numbers 0, 2.5, 5, 7.5 and 10 indicate the weight percentage of llers (CNF) used. The aqueous suspension of the various proportions of CNF, latex and the crosslinking agents were mixed by ball milling followed by ultra sonication. The ball milling process was conducted for 2 h in water medium with ceramic balls (1.5 cm diameter) in stainless steel container (1 l). The speed of the mill was 300 rotations per minute. It is then subjected to ultra-sonication for 10 min in 50 % amplitude at room temperature. The mixed aqueous suspension of the nanocomposites poured into glass plates and dried for 24 h at oven with a temperature of 5060 C in order to obtain dry lms between 1 and 2 mm thick depending on the test and with weight fractions of CNF within the NR matrix ranging from 0 to 10 wt%. Resulting lms were conditioned at room temperature in desiccators containing P2O5 until tested.

of 1.0 Hz and 512 lines per 5 lm was used to optimum contrast. Fourier transform infrared spectroscopy (FTIR) Fourier Transform-Infra Red spectroscopy (FTIR) spectra of the bers were recorded by a Shimadzu IR470 IR spectrophotometer. X-ray diffraction analysis X-ray diffraction was performed using a Bruker AXS X-ray diffractometer equipped with a ltered CuKa radiation source (k = 0.1542 nm) at the operating voltage and current of 45 kV and 40 mA, respectively and a 2D detector. Mechanical testing Tests for measuring the tensile strength were carried out according to ASTM designation D 412-98 using dumb-bell specimens. Rate of separation of poweractuated grip was 500 mm/min, which was maintained throughout the experiment. DMA analysis The dynamic mechanical thermal analysis was conducted using rectangular samples with dimensions 35 9 10 9 2 mm on the DMTA machine of the TA instrument. The experiment was conducted at the frequency of 1 Hz in the temperature range of -80 to ?100 C.

Methods Scanning electron microscopic (SEM) analysis SEM analysis of the samples were done by an Analytical Scanning Electron Microscope (A-SEM), ZEISS EVO 60. The Microscope works with tungsten lament and maximum acceleration voltage of 20 kV. The samples were mounted on aluminium stabs and gold-coated with a sputter coater. Atomic force microscopy (AFM)

Results and discussion The morphological study of the CNF and composites were performed by atomic force microscopy (AFM). The AFM images were made with a Multimode AFM (Agilent Inc. Santa Barbara, USA) with a Nanoscope IV controller in tapping mode at room temperature. A dilute solution of CNF dispersion which was sonicated just before the experiment was used. A drop of CNF suspension was deposited onto a freshly cleaved mica surface and air-dried. For the evaluation of the dispersion of CNF on the composite, a suitable knife was used to cut the inner part of the sample and placed on the mica surface. The silicon nitride cantilever with a spring constant of 40 Nm-1 was used. The scan rate Morphological analysis of CNF and nanocomposite lms Morphological analysis of the CNF which is isolated from banana bre by steam explosion process was conducted by AFM and is shown in Fig. 1. The diameter of the individual nanobres is ranging from 5 to 20 nm. The morphology of NR/CNF composite materials and the distribution level of the ller within the matrix were evaluated by SEM and AFM and are shown in Figs. 2 and 3, respectively. Fractured surface of nanometric reinforced rubbers were observed by

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Fig. 1 AFM image of the cellulose nanobre

SEM in order to know how particles were oriented inside the composites together with the possible examination of rubber-nanobre bonding after the mechanical evaluation. SEM of the tensile fracture surface of 2.5 % CNF nanocomposite (Fig. 2) reveals that the reinforced CNFs are coated with NR latex. CNF appear like white tubes, whose concentration is a direct function of the cellulose content in the composite. We can observe that the distribution of the ller in the matrix is almost homogeneous but some agglomeration of the nanollers which is evident from SEM analysis. The bre pull out is not observed in the

Fig. 2 SEM of the tensile fracture surface of 2.5 % CNF nanocomposite

SEM picture but the CNF is embedded in the rubber matrix. On the other hand, the microphotographs of the fracture surface of the samples indicate that CNF are well dispersed in the rubber matrix and fractured surfaces did not show a high concentration of defects like broken particles or detached particles as in the microcomposites of earlier reports (Ismail et al. 2002), most likely as a consequence of nanomeric size of the celluloses and the strong interaction between the matrix and the ller. Furthermore, no particular sedimentation phenomenon of CNF within the thickness of the lms was observed during the composite preparation. AFM analysis of the inner part of the nanocomposite enabled more detailed information about the dispersion CNF in the rubber latex matrix. The Fig. 3 shows the presence of a homogeneous dispersion of CNF along with some agglomeration of nanobres in the composite. Most of the CNF were dispersed in the 1040 nm range as evaluated by SEM data. But some parts show some agglomeration with a range of 200400 nm range because AFM is more sensitive in its resolution at nanometer dimension than SEM. The agglomeration is more pronounced with the increasing of CNF percentage. NR has a dielectric constant value of 250 and CNF has *3,000 at 1,000 Hz frequency (Carter et al. 1946). The difference in the polarity of the matrix and ller makes this agglomeration which will denitely affect the physical interaction between the ller and the matrix. The CNF appeared signicantly broader having a rounded shape (Deepa et al. 2011). It was therefore difcult to judge whether the structures observed in the AFM were individual nanobre or several nanobres, agglomerated side-by-side. The latter is reected in the measured length of the nanobres. An estimate of the width of the CNF by AFM was not obtained due to the broadening effect and possibly agglomeration of the nanobres in the natural rubber matrix. Comparing with the neat matrix (Fig. 3a), the darkened portions are the reinforced nanollers. The AFM of the nanocomposite (Fig. 3b) has some white portions which represent the 400500 nm dimensions and the agglomerated nanobres might have some contribution to this area. The ndings from the agglomerated nanobres as marked in the SEM (Fig. 2) and the evaluation of the mechanical properties leading to the conclusion for the agglomeration of the nanobres in the reinforced nanocomposites.

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Fig. 3 AFM image of the (a) neat matrix and (b) 10 % CNF nanocomposite

Deprotonation of cellulose and formation Zncellulose complex It is reported that the cellulose can be dissolved in aqueous solvent systems containing metals such as copper and zinc in Cuam and Cuen solutions (Klemm et al. 1998). The dissolution mechanism involves deprotonation of C2OH and C3OH during the metal complex formation. The deprotonation of cellulose is taking place at alkaline medium with the presence of copper and zinc (Ning-Jun et al. 1994). Centrifuged latex, the matrix, whose pH is 11, will make the favorable atmosphere for the deprotonation of cellulose. It is reported that the formation of a zinc cellulose complex during the pre-treatment of cellulose improves the yield of cellulose in both the enzymatic and acid hydrolysis of cellulose (Cao et al. 1995). The spectral characteristics of aqueous zinc chloride solutions containing cellulose were also reported (Xu and Chen 1999). The results suggest that zinc ion forms loose complexes with the C2 or C3 hydroxyl groups of glucopyranose. The high solubility of cellulose in amine containing copper (II) and Zinc (II) is well known (Arthur et al. 1971) but the exact role of Cu (II) and Zinc (II) in cellulose dissolution process and the nature of the Cu (II) and Zinc (II) coordination are ill-dened. The formation of a transient cellulose-zinc is reported by researchers (Calvin 2000) and the deprotonation of the cellulose taking place with the formation of a complex ion with metal. The accelerators and crosslinking agents like Zinc dithiocarbamate (ZDC), zinc mercaptobenzothiozole (ZMBT) and zinc oxide (ZnO) were

used in the nanocomposite preparation stage to generate active sites in the NR backbone for the crosslinking of the matrix. These accelerators not only make active sites in the NR backbone by breaking the C = C double bond but also have a major role in the deprotonation of the CNF and make them participate in the crosslinking network. The ball milling process is applied for the mixing of the CNF, crosslinking agents and NR latex. After mixing the correct formulations of components, the mixture is subjected to ball milling for 2 h. It is then subjected to sonication for 15 min at 50 % amplitude at room temperature. The mechanism of ball-milling followed by sonication caused an increase of amorphous phase of cellulose. The deprotonation of cellulose is difcult by mechanical agitation but ball milling followed by ultra-sonication will make suitable atmosphere to induce reaction sites in the cellulose molecule (Zhang et al. 2008) for de-protonation in the presence of alkaline zinc solution. The ball milling followed by ultra-sonication of the composite mixture will activate the cellulose for deprotonation and weakens inter- and intramolecular hydrogen bonding (Biswas et al. 2005). It is reported that cellulose can be preactivated via ball-milling and they described a two-step mechanism for the synthesis of cellulose-MAPP by a mechano-chemical process (Qiu et al. 2004). In this study, a similar mechanism might be assumed. Under ball-milling, cellulose bers dispersed into nano particles whose specic surface area increased remarkably which favoured chemical reactions with other reagents. Besides, ball-milling followed by ultra-sonication caused an increase of

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amorphous phase of cellulose, making favourable atmosphere for the breakage of inter and intramolecular hydrogen bonds which could produce a large number of free OH groups at the surface of CNF. The resultant OH groups at the cellulose surface were activated, and could form complexes with Zinc (II) during pan-milling. The incorporation of llers causes interruption in the alignment process of chains. When ller loading is increased, weak interfacial regions between ller surface and rubber matrix are formed. The resultant Zncellulose complex diminishes the crystalline nature of the composite and dispersed with metal ion (Abraham et al. 2012). A reaction mechanism is suggested and is shown in Fig. 4. XRD analysis of the NR/CNF composites X-ray patterns were collected for different compositions of NR/CNF and are displayed in Fig. 5. The diffractograms of unlled natural rubber and pure CNF were added as references. The diffraction pattern recorded for a lm of pure CNF obtained by pressing freeze-dried nanobres displays typical peaks of A-type amylose allomorph (Xu and Chen 1999). It is characterized by a strong peak at 2h = 17.9, a very

strong peak at 25.07. The natural rubber lm displays a typical behavior of a fully amorphous polymer. It is characterized by a broad hump located around 2h = 18. By adding CNF, the peaks corresponding to A-type amylose allomorph completely disappear and this is unexpected. This shows that during the composite formation with CNF, the natural rubber and cross linking agents makes some additional chemical interactions with the CNF which leads to the loss of crystalline nature of the cellulose as well as the entire composite. The proposed reaction mechanism between the matrix, ller and crosslinking agents are shown in Fig. 4. The crystalline peak of the cellulose is completely absent for all the composite composition. Under the experimental conditions, there is a perfect agreement between the parallel chain arrangements in the crystals of CNF. The rubber makes chemical bonds with CNF through Zncellulose complex which will result in the loss of its crystallinity. The ller and the cross linking agents enter in between the layers of natural rubber making new bonds with each other. The breaking of one C = C bond in the natural rubber back bone makes two active sites and a cross linking network between sulfur and natural rubber. In addition to that cross linking

Fig. 4 Proposed mechanism for interaction of the cross linked NR/CNF nanocomposite

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Fig. 5 XRD analysis of the nanocomposites

network, cellulose units makes additional network of bonding with zinc to form a zinccellulose complex. This makes the clear dispersion of the CNF in the layers of rubber latex which will leads to the loss of crystallinity of cellulose in the composite entity. Fourier transform infrared (FTIR) analysis The FTIR transmittance spectra of NR and its composites with CNF are shown in Fig. 6. The transmittance spectra, 3,340 and 3,400 cm-1 are the peaks attributed to the stretching vibrations of the hydroxyl group of CNF and 10 % CNF composite respectively. The adsorbed water has also some contribution to the corresponding peak and its intensity is attributed to the three hydroxyl

Fig. 6 FTIR spectra of the nanocomposites

group present in each cellulosic unit. There is a gradual increase in the intensity of this peak on the nanocomposites with the increase in percentage of CNF which is expecting. As already discussed, during the composite formation, in addition to the physical interactions, there are some weak chemical reactions taking place between zinc metal and CNF. The corresponding spectrum of CNF is blue-shifted to 3,400 cm-1 in the spectrum of the composite and the hydroxyl groups of CNF might have some important role in this shift. These phenomena conrm that CNF is successfully activated by crosslinking agents to react with accelerator, zinc metal to form zinccellulose complex. The stretching vibration of methane (2,932 cm-1) which is attached to the isoprene backbone is pronounced in the spectra of natural rubber. The vibration of the methyl group is one of the reasons for the amorphous nature of natural rubber. The intensity of the CH3 and CH vibration which gives a strong peak at 2,932 and 2,896 cm-1 gradually increases with the percentage of the reinforcing ller, CNF. The nanocomposites of NR/CNF give more freedom to the side chain CH3- for vibration because of the presence of Zncellulose complex in between the molecular chains of NR. The breaking up of double bond in the polyisoprene units also gives some relief to the side chain CH3- molecule for vibration. It is observed that there is an increase in the intensity of the CH2 stretching vibration at 2,949 cm-1 and CH stretching vibration at 1,700 cm-1 for the composite. This suggests the breaking up of C = C bond of the NR backbone and a comparative relaxation in the adjacent CH2 and CH bonds. The strong peak at 2,896 cm-1 which is present in CNF is completely absent in all the nanocomposites. The absence of this CH stretching vibration peak characterizing the hydrogen bonds between cellulose chains, suggests the breakage of inter-molecular hydrogen bonds during reinforcing CNF. The free hydroxyl groups of CNF are expected to establish new hydrogen bonds with the other neighboring CNF molecules during the compounding process, leading to a more robust three dimensional network of reinforcing ller in between the rubber phase. The rubber particles are already interconnected by the cross linking agents and resulting a composite with improved mechanical and dynamic mechanical properties. In addition to hydroxyl density which is at 3,400 cm-1, the intensity of transmittance bands at 832, 1,247 and 1,725 cm-1 is also pronounced in the

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IR of natural rubber (Freire et al. 2011). The vibrations of C = O stretching peak at 1,671 cm-1 is almost absent in natural rubber but its intensity shows a gradual increase with increase in the percentage of CNF which reveals the formation of the complex. Mechanical properties of the composite The importance of CNF reinforced composites of polymeric materials comes from the substantial improvement of strength and modulus which gives the suitable application of the composites in various elds. The mechanical properties of the natural rubber and its nanocomposites at different ller loading are shown in Table 2. At room temperature, unlled NR shows a highly elastic non-linear behavior typically of elastomeric materials. Its elongation at break and the tensile modulus was higher than 900 % and lower than 2 MPa, respectively. A decrease of the elongation at break and signicant increase of both the Youngs modulus and strength were observed upon adding cellulose nanoparticles. The presence of hydroxyl groups in the CNF is responsible for the inherent hydrophilic nature of the nanocomposite. Since the matrix, NR latex is in its liquid aqueous form with its highest tendency of hydrophilicity, the compatibility between the hydrophobic natural rubber and hydrophilic CNF is compromised to some extent during the compounding stage. As a result, it becomes very easy to compound CNF dispersion with natural rubber latex along with other cross linking agents which are in aqueous medium. This results in an efcient nanocomposite with good interfacial interaction. As the NR is reinforced with CNF, some interactions are formed between the ller and the crosslinking agents and thereby matrix, (Fig. 4) which consequently increase the mechanical properties (Jamil et al. 2006;

Table 2 Mechanical properties of NR and its composite with CNF: Young modulus (E), tensile strength (rR) and strain at break (eR) Material Natural rubber 2.5 % nanocomposite 5 % nanocomposite 7.5 % nanocomposite 10 % nanocomposite E (MPa) 1.3 0.15 4.2 0.25 6.3 0.22 8.1 0.35 9.6 0.31 rR (MPa) 1.6 0.20 5.2 0.15 6.8 0.18 9.8 0.24 12.2 0.36 eR (%) 912 19 576 23 413 22 275 12 144 5

Siqueira et al. 2011). The mechanism suggests a three dimensional network of NR/Zn/CNF which increases the mechanical properties of the composite. Of the three hydroxyl groups present in cellulose, a hydroglucose unit, one is primary hydroxyl group at C 6, while the other two are secondary hydroxyl groups at C 2 and C 3 positions. A three dimensional network of CNF is formed within the composite entity and this network is formed by reacting with these hydroxyl groups. Due to this three dimensional network between the CNF, the interfacial bonding and mechanical interlocking between the nanobre through crosslinking agents to matrix is increased in the resultant composite. This in turn increases the tensile strength of the composites at all mixing ratios compared to that of neat NR. The decreased crystalline nature of the composite which is evident from the XRD leading to the deterioration of the mechanical performance of the composites. But the enhancement of these properties upon addition of CNF makes clear that the proposed mechanism with the three dimensional network of CNF/Zn/NR dominate over the crystalline nature of the composite when mechanical stress is applied. More over an increase in the CNF content increases the interaction sites between ller matrix. The specic surface area of the ller in contact with the matrix is also increased. As a result, the values of tensile strength show an increasing trend with increasing nanobre content in the composite. The enhanced interfacial bonding will increase stress transfer efciency from the matrix to the ller with a consequent improvement in the mechanical properties of the composites. Of the studied nanocomposites, a maximum tensile strength is shown by composites with loading 10 % CNF. Beyond 10 % CNF concentration, the composite preparation is difcult since the matrix is not sufcient to reinforce the nano bre. The addition of the ller is expected to increase the modulus of composites that results from the inclusion of rigid ller particles into the rubber matrix as reported by Swedish group (Visakh et al. 2012). It is clear from the Table 1 that with the increase in the CNF content in the matrix results a tremendous increase in the modulus of the composites. The Youngs modulus of the 10 % nanocomposite is six times higher than the modulus of neat matrix. Usually crystallites possess higher modulus compared to amorphous substances (Karmakar et Al. 2007). Furthermore, incorporation of ber into the polymer matrix reduces the matrix mobility, resulting in stiffness of the composite. As a result, Youngs modulus increase with

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increasing the ller content of the composites and the percentage of the elongation is regularly decreased with increasing the cellulose content. The gum rubber shows a 900 % elongation but the 10 % nanocomposite shows *140 % of elongation. In conclusion, the interactions between the CNF and the Zncellulose complex have a major contribution in the increment of the stress level of the composite. As described above, CNF are highly strong materials compared to other types of llers like Kevlar and are good candidate to replace conventional bres (Liu et al. 2011). Under load, the matrix distributes the force to the CNF which carry most of the applied load. The synergic effect of rubberrubber, rubber-cellulose, Zncellulose and cellulosecellulose interactions give excellent mechanical properties to nanocomposites. Dynamic mechanical analysis of NR/CNF composites Dynamic mechanical analysis (DMA) is carried out to study the composite structure and performance under various temperatures. Figure 7a shows the storage modulus (E0 ) and Fig. 7b shows the tangent of the loss angle (tan d) at 1 Hz as a function of temperature for the NR matrix and nanocomposites reinforced with CNF. Earlier studies did not observed important changes in the Tg of nanocomposites reinforced with cellulose nanollers. This result was surprising due to the high specic area of such nanollers, (Angles and Dufresne 2000; Samir et al. 2004; Morandi et al. 2009). The increase in values of E0 with ber loading indicates that mobility of the polymer chain is decreased in the presence of bers and here also the change in Tg is comparatively negligible. The curve corresponding to the unlled NR matrix is typical for fully amorphous high molecular weight thermoplastic polymer. The sharp decrease observed around -75 C corresponds to the main relaxation phenomenon and it is therefore associated to the inelastic manifestation of the glass transition. In this temperature range, the loss angle passes through a maximum (Fig. 7b). It is interesting to note that at the low temperature, i.e., below Tg, the reinforcing effect of cellulosic nanoparticle is high. The exact determination of the glassy modulus depends on the precise knowledge of the samples dimensions and at room temperature, the lms were relatively soft and it was difcult to obtain a constant and precise thickness of these samples. Above Tg, a

Fig. 7 a Effect of bre loading on storage modulus of the nanocomposites. b Effect of bre loading on the tan d of the nanocomposites

much more signicant reinforcing effect of the nanoparticles with the ller percentage was observed up to -55 C. This reinforcing effect could be assigned as already reported in the literature to a mechanical percolation phenomenon of cellulose nanobres. Above the percolation threshold, these nanobres connect and form a stiff continuous three dimensional network linked through hydrogen bonding (Dufresne 2008). This is another evidence for the existence of the three dimensional CNF in the proposed mechanism in Fig. 4. This effect was well predicted from the adaptation of the percolation concept to the classical seriesparallel model. In this model and at sufciently high temperature, i.e., when the modulus of the matrix is much lower than the one of the percolating network, the elastic modulus of the composite is simply the product of the volume fraction and modulus of the rigid percolating network. It has been observed that the incorporation of solid crystalline ller into a polymer matrix may increase or

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decrease the mechanical damping of the polymer (Otaigbe 1991). In the present study also, Fig. 7a, it was seen that, E of all the nanocomposites are greater than that of gum rubber. Fiber incorporation increases the storage and loss modulus, which indicates the higher heat dissipation in the CNF reinforced NR nanocomposites compared to that of gum rubber. The storage and loss modulus of nanocomposites exhibits a signicant drop in the transition zone and the intensity of the peaks varies with ber loading. It was observed that in conjunction with the E values, tan d values of the gum natural rubber is much higher than those of the composites with 2.5, 5, 7.5 and 10 % CNF at the experimental frequency. The Fig. 7b shows the lower peak in tan d curves of composite with 10 % CNF loading. The nanocomposites exhibit an enhancement of the modulus at lower temperature range, indicating the elastic responses of pure NR towards deformation and are strongly inuenced by the presence of cellulose dispersion. This behavior also reects the strong connement of CNF dispersion on the rubber molecules and the existence of a Zncellulose complex. Increasing the amount of CNF successively 0 increases the values of E , and the composite with 10 % CNF shows highest modulus. The storage modulus below the transition region shows a difference based on nanobre content where as above the transition there is no improvement is observed contrary to other researchers (Dufresne et al. 1996) ndings. But the mechanical properties like tensile strength and modulus have a positive improvement above the transition region. In the mechanical analysis, the strain was macroscopically homogeneous and uniform along the sample, until its break. The samples exhibit an elastic nonlinear behavior typical of amorphous polymer at T [ Tg. The stress continuously increases with the strain. The polymeric matrix is in the rubbery state and its elasticity from entropic origin is ascribed to the presence of numerous entanglements due to high molecular weight chains and the proposed double network (Zncellulose complex and rubber/rubber). Contrary to DMA experiments, tensile results which is done at room temperature show a higher reinforcing effect for CNF lled NR matrix. This discrepancy could originate from the fact that dynamic mechanical measurements involve weak stresses. The possible interactions of Zn/cellulose network and the rubber/ rubber network are not damaged and/or recorded under these weak stresses. Under the higher stress level, as

applied in tensile tests, these interactions seem to be partially destroyed or highly disturbed. More over Dufresne et al. prepared composite without cross linking agents and hence the possibility of these networks are absent. This is another evidence for the strength of the rubber/rubber and Zn/cellulose network in the cross-linked NR matrix which is higher in tensile tension than that in the unvulcanized sample. The chemical cross-linking of the matrix most probably interferes and strengthen the formation of the Zn/cellulose network which is more pronounced at higher (room) temperature analysis.

Conclusion Nanocomposite materials were obtained by casting and evaporating a mixture of NR latex and aqueous suspension of cellulose nanobrils which is obtained from banana bre by steam explosion. The ller was evenly distributed in the composite structure which is evident from SEM and AFM analysis. The increase of CNF content in the NR matrix causes a drastic inuence in the mechanical properties of the composite, increasing the Youngs modulus and tensile strength of materials, but decreases the characteristic rubber elongation. XRD analysis reveals that the nanocomposites of NR with CNF as ller along with the cross linking agents will lead to the loss of crystallinity of the whole composite because of the nanolevel dispersion of the latter. The formation of a Zncellulose complex and the three dimensional network of the ller is anticipated as a result of the deprotonation of the cellulose, during the composite formation which makes the nanocomposites with good mechanical and dynamic mechanical properties. The enhancement in modulus of the composites even below the glass transition temperature of NR proves the strong reinforcing tendency of CNF in the NR latex matrix. The strong stress level involved in DMA experiments is sufcient to explain the extent of reinforcing effect of cellulose in NR latex matrix.

References
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