Investigation of the Inuence of Processing Conditions on the Thermal, Rheological and Mechanical Behavior of Polypropylene Nanocomposites

H. Mattausch,1 S. Laske,1 I. Duretek,1 J. Kreith,2 G. Maier,2 C. Holzer1 1 Department of Polymer Engineering and Science, Chair of Polymer Processing, Montanuniversitaet, Leoben, Austria
2

Material Center Leoben Forschung GmbH, Leoben, Austria

The use of polypropylene (PP)-layered silicate nanocomposite has attracted great interest in the polymer industry over the last years. On one hand, PP is widely used in many elds of applications because of good performance and cost. On the other hand, the major advantage of layered silicate nanoller in the polymer matrix is the small amount of ller (<5 wt%) needed to enhance various properties such as Youngs modulus. The most commonly used layered silicates are organomodied montmorillonite (MMT). In this study, a PP/ organoclay nanocomposite, lled with layered silicate Nanol SE3010 (1 and 5 wt%), provided by Rockwood Additives, USA, was used. The polymer nanocomposites were prepared via melt intercalation in a laboratory kneader. The compatibilizer (PP grafted with maleic acid anhydride) admixture content relative to the organoclay content (1 and 5 wt%) was chosen at a ratio of 1:1 (clay:compatibilizer). The inuence of different processing conditions (rotation speed and residence time) on the thermal, rheological, and mechanical properties and the interlayer distance was investigated. It was the target to determine whether a short and intensive or a long and soft process performs better. Different properties prefer different states of dispersion of MMT in the polymer matrix. POLYM. ENG. SCI., 00:000
000, 2012. 2012 Society of Plastics Engineers

INTRODUCTION In the last years, the use of polypropylene (PP) nanocomposites (PNCs) has been increased in the industry. This has several reasons. PP as matrix has the benet of low cost and the huge eld of applications. A possibility to enhance properties of PP, such as low toughness, is the use of nanollers. First of all, layered silicates, like montmorillonite (MMT), have a large industrial value because
Correspondence to: S. Laske; e-mail: stephan.laske@unileoben.ac.at DOI 10.1002/pen.23350 Published online in Wiley Online Library (wileyonlinelibrary.com). C V 2012 Society of Plastics Engineers

of their high-aspect ratio, plate morphology, intercalative capacity, natural abundance, and low cost. The most commonly used layered silicate is MMT, which is a member of the smectite group, and has a 2:1 structure: two tetrahedral sheets of silica are connected with one octahedral sheet of alumina or magnesia [14]. The main advantage of nanollers in comparison with microllers is the signicant smaller amount of ller needed to reach or exceed the same property prole. But, for this reason, a good compatibility between the nonpolar PP and the polar nanoller is required, which can be achieved, for example, with the use of a small amount of maleic acid anhydride-grafted PP (PP-g-Ma) as compatibilizer. Two particular characteristics of layered silicates are helpful for good dispersion in the polymer matrix. On one hand, the layered silicates have the ability to disperse into individual layers. On the other hand, the surface chemistry of the layered silicates can be changed via ion exchange reactions with organic and inorganic cations [3, 4]. The processing of PNCs via melt intercalation is the most preferred method to produce polymer nanocomposites (PNCs) for commercial use. The polymer is mechanically mixed with the clay in a two-step process. First, the transportation of the polymer chains inside the silicate layers with the help of a compatibilizer and the weakening of the bonding forces are important. Second, the exfoliation of the weakened layers under shear stress and homogenous dispersion in the melt plays a decisive role. So, the essential factors, which are inuencing this two-step process, are the shear rate and the residence time. These two mechanisms can also take place parallel to each other. Despite the importance of melt intercalation, the effects of processing conditions on the materials properties are not studied very extensively [5]. Most studies deal with the MMT modication and the better dispersion of organoclay in the polymer matrix and also different compatibilizers besides PP-g-Ma were investigated [612]. A novel approach to prepare PP nanocomposites

POLYMER ENGINEERING AND SCIENCE -2012

with OH groups as compatibilizer was rst reported in 1997 [13]. The Toyota research group developed the rst commercial product of clay-based PNCs based on polyamide (PA) 6 in the early 1990s [4, 14, 15]. Olen nanocomposites lled with MMT were produced by General Motors and partners Basell, Southern Clay Products, and Blackhawk Automotive Plastics rst [4]. Dennis et al. [16] showed that the improvement of PA 6 nanocomposites properties depends on the combination of the chemical treatment of the layered silicates and the optimized processing. Davis et al. [17] worked on the inuence of different mixing times and screw speeds at polyethyleneterephthalate MMT nanocomposites. The author discovered that alternative conditions, longer residence times and higher screw rotation speeds led to a lower quality of the nanocomposites [17]. Modesti et al. [18] investigated the inuence of compatibilizer and processing conditions on the morphology and mechanical properties of PP nanocomposites. It was found out that the shear stress is much more important than the residence time, because the diffusion process (dependent on the residence time) is not the controlling factor. The best results were achieved with higher screw rotation speed and lower barrel prole temperature [18]. Lertwimolnum and Vergnes [19] presented a research work of the inuence of compatibilizer and processing conditions on the morphology of PP nanocomposites. The authors showed that the state of intercalation is globally unaffected by the processing conditions. The exfoliation was only improved by increasing shear stress, mixing time and decreasing mixing temperature [19]. Meng et al. [20] applied that the exfoliation of organoclay platelets in PA12 matrix is dependent on the combination of shear and molecular diffusion. In the initial period of mixing, the polymer chains diffuse between the silicate layers. It was already presented in literature that the delamination level of MMT is not the solely factor for the nanocomposites properties. It is also stated that exfoliation is not always advantageous for the enhancement of properties. On the hand, barrier and ame properties need a higher level of delamination, and, on the other hand, mechanical properties increase with intercalated structure [2124]. A study showed that the 3D structure of the layered silicate network is very sensitive to shear deformation. After 10 rad/s, the original structure of the PNCs does not exist anymore [25]. Mohan and Kanny [26] showed that the melt viscosity increases with the addition of MMT in PP. The nanoclay acts as nucleating agent due to the increase in crystallization and rate of crystallization. The kinetic study investigated reduced nucleating effect of nanoclays in higher molecular weight PP samples. The authors also reported that low-shear force and agglomeration of particles decrease the tensile properties of melt-cast samples overextruded composite and that the distribution of MMT is
2 POLYMER ENGINEERING AND SCIENCE -2012

depended on molecular weight of the polymer, processing or synthetic conditions [26]. Pavlidou and Papasyrides [4] reported that various factors can inuence the properties of PNCs. These factors include the type of polymer, layered silicates and organic modier, the preparation technique and processing conditions. The author also summarized that signicant improvements such as mechanical and barrier properties, thermal stability and ame retardance were established with exfoliated structures [4]. Furlan et al. [5] showed the importance of the screw geometries on the property prole of the PP nanocomposite lled with MMT. The difference could be observed in the morphology and in the mechanical properties. The more aggressive screw geometry was disadvantageous for that property prole. With higher shear work, more exfoliated structures were formed. The best mechanical values were achieved with medium shearing. Because of the various discrepancies in literature, also in single publications [19] and the insufcient studies of the structureprocessproperty relationships of PP nanocomposites processed at laboratory scale, this research work was done. The objective of this study is to explore the inuence of residence time and shear rate on thermal, rheological, and mechanical properties and the interlayer distance of the layered silicate particles. Also, a conclusion should be given, whether a soft and short or an intensive and long processing (regarding, for example, shear work) is more effective for a special property. An intensive and short processing should deliver the same results as soft and long processing, if their inuence is even. But, in reality, there is always one factor dominating (e.g., intercalation is a strongly time dependent diffusion process). A long residence time during processing favors a more intercalated PNC system, while more intensive shearing leads to the formation of more exfoliated systems [27, 28]. EXPERIMENTAL Materials The PP BB412E with a melt ow rate (MFR) of 1.3 g/10 min; 2308C/2.16 kg was supplied by Borealis, Linz, Austria. The used nanoller Nanol SE3010 was supplied by Rockwood Clay Additives, Moosburg, Germany. The basic treatment of this modied MMT was made with dimethyl-dihydrogenated-tallow-alkyl-ammonium salt. To improve the compatibility between PP and the nanoller, a functionalized PP grafted with maleic anhydride Scona TPPP 2112 GA (MFR of 37 g/10 min; 1908C/2.16 kg), which was supplied by Kometra, Schkopau, Germany, was used. Preparation of PP Nanocomposites The PNCs were prepared via melt intercalation in a Haake Polylab System 3000P laboratory kneader from Thermo Fisher Scientic, Waltham, USA. The kneading temperature was at 1758C. The kneading time (5, 15, and
DOI 10.1002/pen

25 min) and the rotation speed (60, 90, and 120 rpm) were varied. The kneading times were measured from the time of adding the nanoller. Two different levels of nanollers (1 and 5 wt%) were used. The compatibilizer admixture content relative to the organoclay content was chosen at ratios (clay:compatibilizer) 1:1. The experimental design is illustrated in Table 1. For the various analysis methods, at least four plates of each adjustment with a thickness of 4 mm (tensile tests) and 2 mm (thermal properties, rheology, and X-ray scattering) were prepared using a hydraulic vacuum press machine (Collin 200 PV, Dr. Collin, Ebersberg, Germany). Thermal Properties The thermal properties were analyzed by a differential scanning calorimeter (DSC) DSC 1, Mettler Toledo, Schwerzenbach, Switzerland. The experiments were conducted under a heating rate of 10 K/min, a cooling of 5 K/min, and under owing nitrogen. The samples were heated from room temperature to 2508C. About 9 mg of sample was placed in sealed aluminium cups. Then the samples were cyclically heated and cooled. For a better comparison, the thermograms were normalized to 1 mg. The degree of crystallinity was determined as the ratio between the melting enthalpies of the samples (arithmetic average of the rst and second heating curve) and the melting enthalpy of the 100% crystalline polymer. The enthalpy value for 100% crystalline PP (209 J/g) grades was taken from Marinelli and Bretas [29]. Rheological Properties The rheological properties of the layered silicates nanocomposites were investigated by using a cone and plate rheometer RMS 800 (Rheometrics, Piscataway, USA). To ensure that the strain used is within the linear viscoelastic range, strain sweep tests were performed for each sample. The storage G0 , the loss modulus G00 , and the complex viscosity g* were measured over a frequency range of 0.1 100 rad/s at 2008C under nitrogen environment. Mechanical Properties The tensile tests were carried out on a Universal Tensile Testing Machine Z010 (Zwick and Co. KG, Ulm, Germany) according to ISO 527-1. The specimens for the tensile tests were milled out of a pressed plate. The data were evaluated using the testXpert II software (Zwick and Co. KG, Ulm, Germany). Morphology The morphology of the PP nanocomposites was observed by transmission electron microscope (80 kV TEM, EM 902, Carl Zeiss Microscopy GmbH, Jena, Germany) at the Core Facility Ultrastructure Analysis of
DOI 10.1002/pen

TABLE 1. Experimental design. PP (wt%) 98 90 98 90 98 90 98 90 98 90 98 90 98 90 98 90 98 90 Nanol SE3010 (wt%) 1 5 1 5 1 5 1 5 1 5 1 5 1 5 1 5 1 5 Rotation speed (rpm) 60 60 60 60 60 60 90 90 90 90 90 90 120 120 120 120 120 120 Kneading time (min) 5 5 15 15 25 25 5 5 15 15 25 25 5 5 15 15 25 25

Sample PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

the Medical University Graz, Austria. The ultrathin samples were cryogenically cut to a thickness of 120 nm at the Institute for Electron Microscopy of the TU Graz, Austria. Interlayer Distance The small-angle X-ray scattering (SAXS) measurements were performed using a Bruker NanoSTAR (Bruker AXS, Karlsruhe, Germany). A two-dimensional X-ray detector was used with a wavelength of 0.154 nm (Cu Ka). The samples were measured in transmission at a temperature of 238C. To avoid the inuence of texture, all scattering measurements were performed on plate samples. The scattering curves were corrected for background scatter, and a Gauss correction was applied. Calculation of the Shear Work for Kneading The engine power (W) was calculated as the ratio between the averaged torsional moment and angular speed. The standardized shear work SNorm (kJ/kg) is made up of the ratio between the engine power (MT * x) multiplicated with the kneadings duration (tk) and the weighted sample (WS). The standardized shear work was averaged over at least four specimens. SNorm MT o tk WS (1)

RESULTS AND DISCUSSION Inuence on the Thermal Properties DSC is a very good method to investigate the effect of processing conditions on the thermal behavior of PP
POLYMER ENGINEERING AND SCIENCE -2012 3

TABLE 2. DSC results of the PNCs. First heating Sample PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 TM1 (8C) 118.2 117.4 117.8 117.7 118.0 118.0 117.9 117.2 118.2 117.9 118.8 117.9 117.8 118.0 118.2 117.9 118.1 117.8 DHM1 (J/g) 0.64 0.72 0.75 0.63 0.70 0.50 0.74 0.82 0.60 0.55 0.51 0.54 0.76 0.56 0.55 0.49 0.48 0.53 TM2 (8C) 166.4 165.9 166.2 166.6 166.1 166.4 166.2 166.1 166.2 166.4 167.2 165.4 166.1 166.5 165.5 166.1 165.8 165.5 DHM2 (J/g) 88.1 93.2 102.0 104.5 101.5 85.2 97.8 100.0 101.3 89.7 83.4 93.2 101.0 91.2 89.2 90.0 91.0 89.8 TM1 (8C) 118.8 118.3 119.1 118.5 119.1 118.9 118.7 118.4 119.0 118.8 119.5 118.7 118.8 118.6 119.3 118.9 119.1 118.9 Second heating DHM1 (J/g) 0.67 0.71 0.63 0.76 0.62 0.40 0.81 0.77 0.74 0.43 0.43 0.44 0.74 0.54 0.52 0.46 0.40 0.48 TM2 (8C) 166.7 166.5 166.5 166.9 166.4 166.9 166.5 166.5 166.5 166.9 167.2 165.7 166.3 166.2 165.8 166.4 165.6 166.0 DHM2 (J/g) 92.9 100.1 105.7 103.0 103.4 88.4 104.0 102.3 103.7 93.6 91.4 90.8 103.0 93.8 92.4 89.7 90.8 91.7 DXC (%) 43.3 46.2 49.7 49.6 49.0 41.5 48.3 48.4 49.1 43.8 41.8 44.0 48.8 44.3 43.4 43.0 43.5 43.4

nanocomposites. Results obtained from DSC measurements for PP nanocomposites are presented in Table 2. According to Hong et al. [30] the rst melting temperature (TM1) can be referred to the formation of the b-phase of PP, because MMT improves the heterocrystallization of these PP nanocomposites. It can be seen that the melting points of these nanocomposites are nearly constant (see Table 2). So, melting points are not the adequate values for detecting important changes regarding the different process settings, which is also reported in Refs. [5, 26]. The increasing melt enthalpies (DH) of the second melting peak (TM2) from rst to second heating can be interpreted as differences in thermal treatment in the kneading process compared to the preparation in the DSC measurements [30]. The crystallinity (DXC) is an important indicator for thermal and mechanical properties of polymer and nanocomposites. The DSC curves show that the highest crystallinity of 49.7% at 1 wt% MMT and of 49.6% at 5 wt% MMT can be achieved both by applying rotation speed of 60 rpm for 15 min (see Table 2). The amount of nanoller has only negligible effect on the nal crystallinity of the PNCs. The dependency of shear work on the crystallinity is displayed in Fig. 1. For 1 wt% MMT, it can be seen that the crystallinity achieves higher values at medium-induced shear work. For 5 wt% MMT, this effect is much less pronounced. Presumably, the nucleating effect of the layered silicates decreases with clay content. Also, Furlan et al. [5] reported this effect but could not explain these characteristics. It can be assumed that single layers restrain the mobility of the polymer chains and therefore the crystallization ability of the polymer matrix [24].
4 POLYMER ENGINEERING AND SCIENCE -2012

Inuence on the Rheological Properties The rheological properties of PNCs provide a fundamental understanding of the processing behavior in different processing methods. Especially llers (particle size, particle shape, etc.) have a signicant inuence on the melt state of the material. So, the rheology is a powerful tool for fundamental insights about the state of dispersion, because the rheological values (storage modulus G0 , loss modulus G00 and complex viscosity g*) are sensitive to the dispersion of the dispersed phase. It offers a method to assess the state of dispersion of PNCs directly in the melt state [19, 28, 3036]. According to Wu and Zheng [37] and Pham et al. [38], a lled polymer system develops a percolation network under oscillatory deformation.

FIG. 1. Dependency of shear work on the crystallinity of PP nanocomposites.

DOI 10.1002/pen

FIG. 2. The storage modulus G0 , the loss modulus G00 and the complex viscosity of the PNC at 60 rpm and residence time from 5 to 25 min.

In Fig. 2 the inuence of different processing conditions (rotation speed of 60 rpm and residence time from 5 to 25 min) on the rheological properties of PNCs is depicted. It can be observed that G0 , G00 and g* decrease with higher residence time. The general decrease of the complex viscosity with increasing frequency can be attributed to the strong shear-thinning behavior of the PNC in the molten state [33, 39]. The reason for the higher enhancement of the complex viscosity at lower frequencies is the change from liquid-like to solid-like behavior [33, 39, 40]. The main reasons for the reduction of melt viscosity in the PNC are not clear according to literature [35, 41]. Degradation (e.g., hydrolysis) in the presence of clay can be excluded for the used PNC system due the DSC results. Presumably, the reduction of the viscosity results in the shear-thinning behavior due to the destruction percolation network. The increase of G0 at lower frequencies is due to the existence of a percolated network microstructure indicating an enhancement in the exfoliation state [19, 33]. Higher values of G00 at low frequencies can be attributed to the percolation of randomly distributed silicate layers due to the anisotropy [3, 34]. So, the processing with 5 min produces the highest level of anisotropy and therefore the increased G00 . At 1 wt% MMT, G0 decreases with about 28% at smaller shear rates and with about 5.6% at higher shear rates. At 5 wt% MMT, the deviation of G0 is higher; at lower shear rates about 38% and at higher shear rates about 19%. G00 and g* behave similarly. At 1 wt% MMT, G00 decreases with about 16% at lower shear rates and at higher shear rates with about 2.3%. At 5 wt% MMT, G00 decreases with about 33% at lower shear rates and at higher shear rates with about 7.6%. At 1 wt% MMT, the complex viscosity gets smaller with about 16% at lower shear rates and at higher shear rates with about 4.9%.
DOI 10.1002/pen

At 5 wt% MMT, g* shows lower values of about 26% at lower shear rates and at higher shear rates about 10%. G0 , G00 and g* increase with the content of nanoller. The differences in the rheological behavior could be attributed to the better homogenization of the more exfoliated PNCs assumedly due to the different state of dispersion [27]. Okamoto et al. [42] suggested a formation of a house-of-card-structure during the ow of layered silicatelled polymer. Another aspect of interpretation of melt state of the PNCs is the Cross Over Point (see Fig. 2). The Cross Over Point is formed by the intersection of the G0 and G00 curves. For unlled polymers, the position of this point gives empirical information about the changes in molecular weight distribution and the average molecular weight. In this work, the concept is also applied on PNCs. With increasing nanoller content from 1 to 5 wt%, the Cross Over Point shifts to a higher frequency. This effect can be explained in the selective absorption of the polymer molecules by the nanoller. Thereby, the remaining polymer molecules, which are not absorbed by the nanoller, are forming the matrix, which have a decreased chain length and molecular weight [43]. With higher ller content, this effect becomes more signicant, and the Cross Over Point shifts to lower apparent molecular weight. From this, a good exfoliation of the nanoller in the PP matrix can be deduced, due to the different formation of absorbed polymer chains to the nanollers surface. Another reason for this shift, the degradation of the polymer chains, can be excluded due to DCS results. With higher ller content, the Cross Over Point also shifts slightly to higher modulus values. This is an indicator for a broader molecular mass spectrum in the residual nonabsorbed matrix polymer. Inuence on the Mechanical Properties For the characterization of the inuence of the processing conditions on the mechanical properties the Youngs modulus, the tensile stress at break and the elongation at break were measured. Youngs modulus was chosen because of the strong inuences of already small amounts of nanoller on the mechanical values. In Table 3, the various mechanical values are presented. It can be observed that a higher amount of nanoller also increases the Youngs modulus. The residence time has marginal inuence on the Youngs modulus. The reason for the improvement of the Youngs modulus has two mechanisms. The rst mechanism, which is also valid for the reinforcement with conventional llers, works through the higher Youngs modulus of the ller that highly restrains the polymer matrix mechanically. This effect becomes more pronounced in intercalated polymer-layered silicate systems. Thereby, the polymer chains are highly restricted in their movements by the closely spaced silicate layers. Because of the increasing degree of exfoliation and so on an increasing space
POLYMER ENGINEERING AND SCIENCE -2012 5

TABLE 3. Mechanical values of the PNCs. Youngs modulus (MPa) 1710 1850 1700 1890 1630 1850 1690 1820 1630 1830 1710 1840 1680 1800 1600 1810 1640 1780 Tensile stress at break (MPa) 19.1 19.8 17.8 19.8 18.9 20.1 19.1 20.1 18.6 20.8 19.0 21.0 18.4 19.6 19.2 20.4 18.7 20.5 Elongation at break (%) 57.7 29.5 57.0 29.2 116.3 30.3 84.7 30.2 64.1 13.0 52.7 7.0 66.8 54.4 63.2 16.4 52.8 16.2

Sample PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS PPS 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

between the single layers, this stiffening effect decreases but remains still a high level. This is highly dependent on the bonding between ller and polymer [4, 21, 36, 44]. The second mechanism explains the dramatic improvement of the Youngs modulus with only a small amount of layered silicates. Pavlidou and Papasyridess [4] theory implies that the polymer chains in contact with the nanoller surface are inuenced by the nanoller itself. These polymer chains develop a much higher Youngs modulus than the polymer matrix around [4]. The highest values of the Youngs modulus are achieved with lower rotation speeds. This can be explained by the low-shear effect of the rotors and the formation of stationary vortexes at the rotors. The outliner at 60 rpm, 25-min residence time, and 1 wt% layered silicate can also be explained by same arguments as mentioned earlier. At 1 wt% MMT, the highest Youngs modulus can be achieved with soft (60 rpm) and short (5 min) and with medium (90 rpm) and long (25 min) processing. The lowest value is measured with intensive (120 rpm) and intermediate (15 min) processing. Also, a soft and long and an intensive and long processing have a bad inuence on this mechanical value. At 5 wt%, the highest value can be observed with soft and intermediate processing and the lowest values with intensive and long processing. The tensile stress at break decreases slightly with increasing clay content, although the signicance of the trend is not that high as for Youngs modulus [4]. Alexandre and Dubois [45] suggested that the tensile stress at break increases with the enhancement of interfacial adhesion. The lack of this adhesion is responsible for constant or decreasing value of the ultimate tensile strength. Therefore, it can be concluded that the interfacial adhesion increases with higher amount of layered silicates, respectively, with proceeded exfoliation. No signicant trend can be observed regarding the applied rotation speed and residence time.
6 POLYMER ENGINEERING AND SCIENCE -2012

At 5 wt% MMT, intensive (120 rpm) and intermediate (15 min) processing achieve the highest tensile stress at break. The lowest value can be achieved with soft (60 rpm) and intermediate (15 min) processing. Generally, there is no signicant difference in the tensile stress at break by short (5 min) or long (25 min) processing for all rpm. At higher nanoller content (5 wt%), the highest tensile stress at break can be obtained by medium (90 rpm) and long (25 min) processing and the lowest value by intensive and short or soft and intermediate processing. The elongation at break is decreasing with increasing nanoller content, which leads to the embrittlement of these PP nanocomposites. In literature, there are several explanations for this brittleness. On one hand, it is explained by the formation of microvoids during debonding processes between the nanoller and the polymer matrix [4, 46, 47]. On the other hand, this could be due to the greater interactions between the nanoller and the polymer matrix, which increases the rigidity through decreasing the mobility of the polymer chains [18]. The variation of the nanoller content has a larger impact on the ultimate elongation than the other varied process parameters. Pavlidou and Papasyrides [4] have also reported that this mechanical value is not that adequate for the analysis of trends. Nevertheless, the importance for industrial processes is not deniable. The highest elongation at break for low (1 wt%) nanoller content is measured with soft (60 rpm) and long (25 min) processing and the lowest value with intensive (120 rpm) and long (25 min) processing. At 5 wt% MMT, the elongation at break achieves with intensive and short processing the highest value. With medium and long processing, the lowest elongation at break can be achieved. In Fig. 3, the inuence of shear work on the Youngs modulus of PNC can be observed. As expected, the results for 5 wt% layered silicate show a higher shear

FIG. 3. Dependency of shear work on the Youngs modulus of PP nanocomposites.

DOI 10.1002/pen

continuous polymer matrix, and, in some areas, individual clay layers are recognizable. At 5 wt% MMT, the achieved interlayer distance shows the lowest values for highest rotation speed, but there is no clear trend. At 1 wt% nanoller content and 5 min residence time, the interlayer distance is independent of the rotation speed. In contrast to 25 min residence time, the interlayer distance shows a signicant decrease at low rotation speed. At 5 wt% MMT, a long (25 min) and intensive (120 rpm) processing is disadvantageous for the interlayer distance. The largest interlayer distance is achieved with medium rotation speed and intermediate residence time. The property enhancement of the PP nanocomposite is related to the interlayer distance of the layered silicates.

FIG. 4. Dependency of shear work on the interlayer distance of PP nanocomposites.

work than for 1 wt% nanoller content. For both loadings, a decreasing tendency with local maxima can be observed. This suggests that only special values of induced shear work deliver morphological states, which favor the stiffening effect of the nanoller.

Inuence on the Interlayer Distance SAXS is an adequate measurement method to determine the morphological structure of MMT particles in the PNC. Thereby, the interlayer distance is the spacing of one particle including the distance to the next particle. According to the material data sheet, Nanol SE3010 has an interlayer distance of 3.6 nm. Also, TEM measurements were carried out to delineate the morphology of the PNC. Figure 4 depicts the interlayer distance for both nanoller contents in dependency of the shear work. At 5 wt% MMT, the interlayer distance is much smaller than the distance of the single silicate layers with 1 wt% MMT. Especially, at the PNC with higher nanoller content, it can be seen that the interlayer distance increases to a certain value, and afterward, the high-induced shear work is unfavorable for the interlayer distance. The induced shear work aids the diffusion of the polymer chains between the single layers of the MMT packs. The clay aggregates become smaller, and silicate layers are nely dispersed in the polymer matrix. This suggests a higher level of intercalation/exfoliation. So, with increasing shear work, rst, a more intercalated and consecutively an exfoliated polymer-layered silicate system is developed. Presumably, the single silicate layers become rearranged into layered silicate clusters under the inuence of shear work exceeding a certain value. In Fig. 5, TEM images of a typical area of the PNC containing 1 (see Fig. 5a) and 5 wt% MMT (see Fig. 5b) are depicted. Both images also show exfoliated structures, thereby the clay layers are separated in a
DOI 10.1002/pen

FIG. 5. TEM images of the PNC containing 1 wt% MMT (a) and 5 wt% MMT (b).

POLYMER ENGINEERING AND SCIENCE -2012 7

CONCLUSION In this work, the PNCs have been prepared on laboratory kneader via melt intercalation. The effects of different processing conditions (such as rotation speed or normed shear work) on the thermal, rheological, and mechanical properties and interlayer distance were investigated. It was observed that processing conditions have differing impacts on the single values of the property prole. The DSC results suggest that this is not an applicable to detect any important changes regarding the processing conditions of PP-layered silicate nanocomposites. Nevertheless, degradation (e.g. hydrolysis) in the presence of clay can be excluded due to the DSC results. A higher crystallinity can be achieved with intermediate residence time and soft-rotation speed for both nanoller contents. The rheological values, which are sensitive to the state of dispersion of the MMT, decrease with increasing rotation speed due to the more exfoliated polymer nanoller system formed by the more intensive shearing. The concept of the cross over point has been applied on PP nanocomposites. Based on these considerations, a good exfoliation of the nanoller in the PP matrix can be deduced, due to the different formation of absorbed polymer chains to the nanollers surface. The Youngs modulus increases with lower rotation speed. The highest Youngs modulus is achieved with short residence time and soft rotation speed at 1 wt% MMT and with intermediate and soft processing at 5 wt% MMT. The best results for tensile stress at break are reached with short and soft processing at 1 wt% and a long residence time and medium rotation speed at 5 wt%. The highest elongation at break values is obtained with a long residence time and soft rotation speed for lower nanoller content and short and intensive processing for the higher amount of layered silicates. For the increasing of the interlayer system, an intermediate residence time and a high-rotation speed at 1 wt% MMT are needed.

FIG. 6. Dependency of interlayer distance on the crystallinity of the PNC.

An exfoliated system is not always the best solution for a particular property prole. The interlayer distance decreases with a larger amount of layered silicates (see Fig. 6). The crystallinity increases up to an optimum interlayer distance. Beyond this range, the crystallinity falls rapidly. At 1 wt% nanoller content, the residence time does not affect the crystallinity. The main inuence factor is the intensity of shearing, where the low and medium-rotation speed achieved the highest crystallinities. At 5 wt% MMT, soft (60 rpm) and short (5 min) to intermediate (15 min) processing increases the crystallinity. The lowest values are achieved with 120 rpm (short to long residence time) and with 60 rpm and 25 min. These results can presumably be explained by the better distribution effect of the rotation speed than the residence time. The inuence of the interlayer distance on the Youngs modulus is shown in Fig. 7. The same trend as for the crystallinity can be seen for the Youngs modulus. The highest values of the Youngs modulus can be achieved with soft to medium (6090 rpm) rotation speeds. At 1 wt% MMT, the residence time has no impact on the Youngs modulus. The lowest Youngs modulus is measured with an intermediate and intensive processing and a large interlayer distance. At 5 wt%, the highest Youngs modulus is achieved with soft (60 rpm) and intermediate (15 min) processing. Especially, the high-rotation speed (120 rpm) is responsible for a low-Youngs modulus and a small interlayer distance. For each investigated clay content, a certain range of interlayer distances is preferable for high-Youngs modulus values. A too large or too short interlayer distance is impedimental for the Youngs modulus. Szazdi et al. [48] and Lai et al. [49] have also illustrated that a high degree of exfoliation may not guarantee high-tensile strength for PNC. Also, Touati et al. [33] have observed that a better dispersion of the MMT in the polymer matrix does not necessarily increase the performance of the PNC due to the negative effect of degradation.
8 POLYMER ENGINEERING AND SCIENCE -2012

FIG. 7. Dependency of interlayer distance on the Youngs modulus of the PNC.

DOI 10.1002/pen

At 5 wt% MMT, the interlayer distance achieves the biggest distance between the layers with intermediate residence time and medium-rotation speed. Generally, the rotation speed (induced shearing energy) has a higher impact on the nal properties of the PP nanocomposite than the applied residence time. The results show that a large interlayer distance is not advantageous for specic desired effects. A more intercalated polymer nanoller system is preferred for mechanical values because the polymer chains are clamped between single layers, and the possible chain movement is more restricted, which increases the stiffening effect of the nanoller. The degree of delamination is highly affected by the organic modier and the applied processing conditions. Although there are many publications about the effects of processing conditions of PP nanocomposites, predictions on the achievable structure are still difcult. ACKNOWLEDGMENTS The authors thank the Chair of Designing Plastics and Composite Materials for the precious help in making the specimens for the tensile tests and the Chair of Materials Science and Testing of Plastics for the tensile tests. Acknowledge of any prior oral presentation and original source of the material: Inuence of processing conditions and induced shear work on the thermal, rheological and mechanical behavior of polymer nanocomposites, In: Proceeding The 27th Annual Meeting of the Polymer Processing Society, Marrakesh, Morocco. REFERENCES
1. M. Modesti, A. Lorenzetti, D. Bon, and S. Besco, Polym. Degrad. Stab., 91, 4 (2006). 2. H. Qin, S. Zhang, C. Zhao, M. Feng, M. Yang, Z. Shu, and S. Yang, Polym. Degrad. Stab., 85, 2 (2004). 3. S.S. Ray and M. Okamoto, Prog. Polym. Sci., 28, 11 (2003). 4. S. Pavlidou and C.D. Papasyrides, Prog. Polym. Sci., 33, 12 (2008). 5. L.G. Furlan, C.I. Ferreira, C. Dal Castel, K.S. Santos, A.C.E. Mello, S.A. Liberman, M.A.S. Oviedo, and R.S. Mauler, Mater. Sci. Eng. A Struct., 528, 22 (2011). 6. D. Shi, W. Yu, R.K.Y. Li, Z. Ke, and J. Yin, Eur. Polym. J., 43, 8 (2007). 7. B. Kandola, G. Smart, A.R. Horrocks, P. Joseph, S. Zhang, T.R. Hull, J. Ebdon, B. Hunt, and A. Cook, J. Appl. Polym. Sci., 108, 2 (2008). 8. S.K. Sharma and S.K. Nayak, Polym. Degrad. Stab., 94, 1 (2009). 9. H.S.A. Khalil and A.A. Abdelhakim, J. Appl. Polym. Sci., 86, 10 (2002). 10. Z. Martin, I. Jimenez, M.A. Gomez, H.W. Ade, D.A. Kilcoyne, and D. Hernadez-Cruz, J. Phys. Chem. B, 113, 32 (2009). 11. C.C. Chu, M.L. Chiang, C.M. Tsai, and J.J. Lin, Macromolecules, 38, 15 (2005).
DOI 10.1002/pen

12. R. Gallego, D. Garcia-Lopez, J.C. Merino, and J.M. Pastor, Polym. Int., 59, 4 (2010). 13. A. Usuki, M. Kato, A. Okada, and T. Kurauchi, J. Appl. Polym. Sci., 63, 1 (1997). 14. A. Usuki, Y. Kojima, M. Kawasumi, A. Okada, Y. Fukushima, T. Kurauchi, and O. Kamigaito, J. Mater. Res., 8, 5 (1993). 15. A. Usuki, A. Koiwai, Y. Kojima, M. Kawasumi, A. Okada, T. Kurauchi, and O. Kaimigaito, J. Appl. Polym. Sci., 55, 1 (1995). 16. H.R. Dennis, D.L. Hunter, D. Chang, S. Kim, J.L. White, J.W. Cho, and D.R. Paul, Polymer, 42, 23 (2001). 17. C.H. Davis, L.J. Mathias, J.W. Gilman, D.A. Schiraldi, J.R. Shields, P. Trulove, T.E. Sutto, and H.C. Delong, J. Appl. Polym. Sci., 40, 23 (2002). 18. M. Modesti, A. Lorenzetti, D. Bon, and S. Besco, Polymer, 46, 23 (2005). 19. W. Lertwimolnun and B. Vergnes, Polymer, 46, 10 (2005). 20. X. Meng, Z. Wang, Z. Zhao, X. Du, W. Bi, and T. Tang, Polymer, 48, 9 (2007). 21. S. Laske, M. Kracalik, M. Gschweitl, M. Feuchter, G. Maier, G. Pinter, R. Thomann, W. Friesenbichler, and G.R. Langecker, J. Appl. Polym. Sci., 111, 5 (2009). 22. M. Kracalik, J. Mikesova, R. Puffr, J. Baldrian, R. Thomann, and C. Friedrich, Polym. Bull., 58, 1 (2007). 23. M. Kracalik, M. Studenovosky, J. Mikesova, A. Sikora, R. Thomann, C. Friedrich, I. Fortnelny, and J. Simonik, J. Appl. Polym. Sci., 106, 3 (2007). 24. M. Kracalik, M. Studenovosky, J. Mikesova, J. Kovarova. A. Sikora, R. Thomann, and C. Friedrich, J. Appl. Polym. Sci., 106, 3 (2007). 25. M. Kracalik, S. Laske, A. Witschnigg, and C. Holzer, Rheol. Acta, 50, 11 (2011). 26. T.P. Mohan and K. Kanny, Mater. Sci. Appl., 2, 1 (2011). 27. M.E. Mackay, A. Tuteja, P.M. Duxbury, C.J. Hawker, B. Van Horn, Z. Guan, G. Chen, and R.S. Krishnan, Sci., 311, 5768 (2006). 28. L. Zhu and M. Xanthos, J. Appl. Polym. Sci., 93, 4 (2004). 29. A.L. Marinelli and R.E.S. Bretas, J. Appl. Polym. Sci., 87, 6 (2003). 30. H.Q. Hong, H. He, Z.X. Jia, C. Ding, and D.M. Jia, J. Appl. Polym. Sci., 102, 4 (2006). 31. J. Ren, A.S. Silva, and R. Krishnamoorti, Macromolecules, 33, 10 (2000). 32. G. Galgali, C. Ramesh, and A. Lele, Macromolecules, 34, 4 (2001). 33. N. Touati, M. Kaci, S. Bruzaud, and Y. Grohens, Polym. Degrad. Stab., 96, 6 (2011). 34. N.T. Dintcheva, S. Al-Malaika, and F.P. La Mantia, Polym. Degrad. Stab., 94, 9 (2009). 35. J.W. Cho and D.R. Paul, Polymer, 42, 3 (2001). 36. M.J. Solomon, A.S. Almusallam, K.F. Seefeldt, A. Somwangthanaroj, and P. Varadan, Macromolecules, 34, 6 (2001). 37. G. Wu and Q. Zheng, J. Polym. Sci., Part B: Polym. Phys., 42, 7 (2004).
POLYMER ENGINEERING AND SCIENCE -2012 9

38. Q.T. Pham, W.B. Russel, J.C. Thibeault, and W. Lau, J. Rheol., 43, 6 (1999). 39. Y. Wang, F.B. Chen, Y.C. Li, and K.C. Wu, Compos., Part B: Eng., 35, 2 (2004). 40. F. Fordiani, T. Aubry, and Y. Grohens, J. Appl. Polym. Sci., 114, 6 (2009). 41. M.R. Thompson and K.K. Yeung, Polym. Degrad. Stab., 91, 10 (2006). 42. M. Okamoto, P.H. Nam, P. Maiti, T. Kotaka, N. Hasegawa, and A. Usuki, NanoLetters, 1, 6 (2001). 43. Z. Dominkovics, J. Hari, J. Kovacs, E. Fekete, and B. Pukanszky, Eur. Polym. J., 47, 9 (2011).

44. T.D. Fornes and D.R. Paul, Polymer, 44, 14 (2003). 45. M. Alexandre and P. Dubois, Mater. Sci. Eng. R, 28, 1 (2000). 46. I.Y. Phang, T. Liu, A. Mohamed, K.P. Pramoda, L. Chen, and L. Shen, Polym. Int., 54, 2 (2005). 47. J. Morawiec, A. Pawlak, M. Slouf, A. Galeski, E. Piorkowska, and N. Kransnikowa, Eur. Polym. J., 41, 5 (2005). 48. L. Szazdi, Jr. B. Pukanszky, G. J. Vancso, and B. Pukanszky, Polymer, 47, 13 (2006). 49. S.M. Lai, W.C. Chen, and X.S. Zhu, Compos., Part A: Appl. Sci., 40, 6 (2009).

10 POLYMER ENGINEERING AND SCIENCE -2012

DOI 10.1002/pen