Study on Effects of Nanosilica Sand Addition on Physical and Mechanical Properties of Polypropylene (PP)

AP Dr. Othman Bin Mamat1, Dzul Khairee Bin Yasaa2

1

Department of Mechanical Engineering, Universiti Teknologi PETRONAS 31750 Tronoh, Perak, Malaysia e-mail: 1drothman_mamat@petronas.com.my, 2ayies88@gmail.com Chun Lei et al [2, 3] investigated the tensile performance improvement of low nanoparticles filled-polypropylene composites and results indicated that the nanoparticles could simultaneously provide PP stiffing; strengthening and toughness effects at rather low filler content (typically 0.5% by volume). The presence of grafting polymers on the nanoparticles improves the tailorability of the composites. Due to the viscoelastic nature of the matrix and the grafting polymers, the tensile performance of the composites filled with untreated and treated nanoparticles is highly dependent on loading rate. It is investigated that particles surface treatment, matrix ductility, nanoparticles size and particle species also affect the mechanical performance of polypropylene based silica nanoparticles composites. The results indicate that graft polymerization onto the precipitated nano-silica is still an effective method to pretreat the particles, which leads to an overall improvement of the composites properties. Chaganti et al [4] stated that the preparation of composite materials by the melt blending of polymers and llers is a straight forward procedure, but it is less efficient when the reinforcing ller is in nanoscale. This is due to an agglomeration of nanoparticles along with the high melt viscosity of the polymers. To overcome these limitations in composite preparation, a rst strategy based on ller encapsulation by polymer coating has been proposed. Another approach relies on the chemical modication of the ller surface by functional silanes and titanate esters, which are able to promote adhesion to the polymer matrix. However, the high cost of functional silane compounds also limits their usage for mass production. Yiqun et al [5] found that the tensile moduli, impact and flexural properties of Thermoplastic Olefin Blend (TPO)/nanosilica composites showed improvements at low loadings of nanosilica, indicating a good balance of stiffness and toughness. Nanosilica filled polypropylene composites are hard to be broken apart during compounding due to the strong interaction among the nanoparticles, the limited shear force provided by the mixing device and the high melt viscosity of polymer melts. This will aect some important properties of the matrix polymers such as appearance, density and process performance. Other than that, this also affects the mechanical properties of the polymers such as the improvement of tensile strength and toughness. Therefore, a

Abstract- The development of polymeric nanocomposites has

widely used in recent years. These nanofillers have great affect on the mechanical, barrier, electrical and thermal properties of base polymers. The present study aims to develop PP matrix composite with silica sand nanoparticles. To examinate the applicability of the study, the silica sand nanoparticles with average particle size of less than 100nm was produced by several stages of ball mill and heating combinations. PP matrix composites with 5, 10, 15 and 20 wt.% of silica sand nanoparticles were developed through internal mixing and then produced by using injection moulding machine. Physical properties, mechanical properties and microstructure were studied. It was observed that physical properties increased with increasing trend of silica sand nanoparticles in PP. The results of tensile tests indicated that the addition of silica sand nanoparticles decreased the tensile strength with increasing trend of silica sand nanoparticles. However an improvement in flexural strength was observed.

I.

INTRODUCTION

Polypropylene is an economical material that offers a combination of outstanding physical, chemical, mechanical, thermal and electrical properties not found in any other thermoplastic. Compared to low or high density polyethylene, it has a lower impact strength, but superior working temperature and tensile strength. Problem that arises for attention is polymer degradation issue. Polymer degradation is a change in the properties tensile strength, colour, shape - of a polymer or polymer based product under the influence of one or more environmental factors such as heat, light or chemicals such as acids, alkalis and some salts. These changes are usually undesirable, such as changes during use, cracking and depolymerisation of products or, more rarely, desirable, as in biodegradation or deliberately lowering the molecular weight of a polymer for recycling. The changes in properties are often termed "ageing". Therefore, polymer degradation is one of major concern in polymer industries which needs continuous attention and improvement.[1] Mineral llers are added to polymers in most commercial production for the reasons of stiness and toughness improvement. Some researchers showed the improvement of toughness can be increased by adding nanoparticles in polymers. It is worth noting that in the case of micrometersized particulates, high ller content (typically higher than 20% by volume) is generally required to bring the abovestated positive eects of the llers into play.[2]

composite with improved performance and low particle concentration is highly required. With regard to this, the newly developed nano composites would be competitive candidates. II. EXPERIMENTAL DETAILS A. Materials and Processing The silica sand was originated naturally from Tronoh Minerals Resources, Perak, Malaysia and ground to nanoparticles by using dry ball mill with zirconia ball (beads) as grinding media. The analysis of silica sand nanoparticles had been verified using the ZetaSizer, ZS Nano (ZEN 3600) (MALVERN) analyzer. Photon correlation spectroscopy (PCS) or dynamic light scattering (DLS), is a technique used to determine particle size by examining the diffusion rates (i.e. Brownian motion) of suspended particles. The technique utilizes a light source to illuminate the samples and scattered light is collected at a detector typically positioned at a fixed scattering angle. The latest generation Zetasizer Nanoparticles analyzer using PCS/DLS instruments, utilize a backscatter angle of 173 degrees. This optical configuration accommodates both high and low sample concentration, low sample volumes. It also reduces the probability of intensity biasing, a phenomenon that occurs in 90 degree systems where the magnitude of light scattered by a large particle overshadows the light collected from the smaller particles. These results are then verified microscopically through Emission Scanning Electron Microscope (FESEM). The chemical composition of silica sand was analyzed by using X-Ray Fluorescence (XRF) technique. TITANZEX Malaysia supplied the commercial grade PP. B. Composites and Samples Preparation 5 samples were produced, namely Pure PP, 5wt%, 10wt %, 15wt% and 20wt% SiO2+PP. Before mixing to PP polymer, silica sand nanoparticles were heated at 200 oC to remove the possible absorbed water for 5 hours. Silica sand nanoparticles were weighted accordingly to weight percentage (wt%) and mixed with PP. The mixing of silica sand nanoparticles with PP was carried by using internal mixer (Thermo Haake PolyLab System) under Roller-Rotors R3000 with 50 rpm and 190 oC temperature for 10 minutes. After mixing the granular shape of the mixed particles were produced using granular machine. The resultant particles were moulded into dog-bone-shaped tensile bars (ASTM D638-97) with Injection moulding machine at 215 oC. The flexural test specimens were also produced by following ASTM D790-03 by Injection moulding machine. Tensile and flexural properties of the composites were measured by Universal Tensile Testing machine (5 KN) LLOYD Instruments, LR 5K. The tensile test for PP-SiO2 samples were performed with a crosshead speed of 50 mm/min. The densities of PP based silica sand nanoparticles composites were measured by using according to ASTM standard D 792.

III. RESULTS AND DISCUSSION A. Morphology, size and distribution analysis of Tronoh silica sand nanoparticles In this work silica sand particles, the macro and microscale were reduced to a nanoscale particle size (which then called as silica sand (SiO2) nanoparticles). The high-energy milling processes involve the comminution of bulk materials. The principle of comminution is centred on applying physical forces to bulk material so as to affect breakage into smaller sizes. The forces required to effect breakage are usually a combination of either impact or shear. Material is introduced into a milling chamber containing grinding media. Milling occurs when the media is made to move either by stirring (using a rotor) or by shaking/vibrating the chamber and contacts the bulk material thus imparting, depending on the milling parameters, either impact or shear forces on it. Breakage can occur through a variety of mechanisms and are generally described as attrition, abrasion, fragmentation or chipping and occur both at the macro and microscopic level [6]. The silica sand (SiO2) particle was quantitatively analysed using ZetaSizer and its result is shown in Fig.1. The average size for the silica particles was found 78.82 nm which was qualified to be considered as SiO2 nanoparticles.

Fig. 1: The average particle size produced by size distribution of intensity is 78.82 nm.

Morphology, size and distribution of the SiO2 sand nanoparticles are shown in Fig. 2. It can be seen that some of SiO2 particulates have fused together resulted from squeezing action of the ball-milling process. The after ballmilled SiO2 nanoparticles formed wide range of shape from irregular or rod-like aggregates and agglomerates to rounded nanoparticles. The high surface energy of nanoparticles SiO2 is responsible for the aggregation. The conglomeration of submicron SiO2 particles is a spontaneous process because the Gibbs energy decreases during this process.

Fig. 2: FESEM image of the silica sand nanoparticles.

The FESEM image in Fig. 2 also illustrates various structures of the SiO2 particles including spherical particles and irregular shape particles as well as agglomerates. This strong tendency for agglomeration exists in the particles was induced by the Van-der-Waals forces acting between the individual particles. The morphology of such agglomerates may vary from chain-like (1-D) to heavily aggregated (3-D). This alone would not constitute a major problem since soft agglomerates held together by Van-der-Waals forces only are easily broken down in the next step of dry pressing that was incorporated in the powder processing. Several primary particles seem to cluster or fuse at their faces, which is possibly due to growth and sintering of individual crystals during the ball-milling process [7, 8]. Chemical composition of Tronoh silica sand nanoparticles The chemical composition of the silica sand was analyzed using XRF analysis following the STG2-S4-Check measurement method. The result is shown in Table 1.
Table 1 Chemical composition of Tronoh silica sand nanoparticles. Compound Weight percentage (wt%) Al2O3 2.99 SiO2 95.22 P2O5 0.77 K2O 0.095 CaO 0.139 TiO2 0.16 Fe2O3 0.121

C. Mechanical Properties of PP-SiO2 composites Mechanical properties of PP-silica sand nanoparticles composites are shown in Table 2. The results showed a decrease in tensile strength however an improvement was found in Youngs Modulus and flexural strength of the composites. Figure 4 shows the fracture tensile test samples of PP-SiO2 composites. A strong filler/matrix adhesion would lead to enhanced strength of particulate composites.[2] According to their consideration, it is known that the improvement of tensile strength of the composites is due to interfacial interaction. The improvement of interfacial interaction will increase the tensile strength of the composites. However, the addition of other particles in PP composites does not always increase the tensile strength. Based on the result obtained, tensile strength of PP-SiO2 composites decreased with the addition of silica sand nanoparticles and become slightly constant for different addition wt% of silica sand nanoparticles (Fig. 5). This was due to poor bonding at the interface between PP and Silica sand nanoparticles. The low of interfacial interaction will result the decrease in tensile strength. Youngs Modulus increased (Fig. 6) because the addition of silica sand nanoparticles increased the interfacial stiffness of the composites. Usually the capability of composite interface to transfer elastic deformation depends to a great extent upon the interfacial stiffness and static adhesion strength. A high interfacial stiffness corresponds to a high composite modulus.[3] As interfacial stress transfer efficiency depends on the stiffness of the interphase, higher interfacial stiffness favors improvement of the composites modulus.[2] Based on the graph obtained (Fig. 7) the increase of weight percentage (wt%) of silica sand nanoparticles increase the flexural strength of the composites. The tensile moduli, impact and flexural properties of thermoplasticolefin blend (TPO)/nanosilica composites showed improvements at low loadings of nanosilica, indicating a good balance of stiffness and toughness.[5] According to the statement, the increase of flexural strength is due to good adhesion between PP and Silica sand nanoparticles. When the bonding is strong enough, the flexural strength of particulate composites can be higher than pure PP.
Table 3: Mechanical properties of PP composites with different wt% of SiO2 Silica Tensile Young's Flexural Sand+PP Max Load Strength Modulus Strength Composites (N) (MPa) (MPa) (MPa) 1505.090 Pure PP 7 37.6273 254.4127 19.894 5wt% 1221.707 SiO2+PP 0 30.5427 242.7426 19.847 10wt% 1193.539 SiO2+PP 9 29.8385 274.3043 20.018 15wt% 1239.249 SiO2+PP 3 30.9812 259.4165 19.963 20wt% 1219.081 SiO2+PP 4 30.477 293.6561 20.09

B. Physical Property (Density) of PP-SiO2 composites From the graph (Fig. 3) an increasing trend of density was observed with the increasing content of silica sand nanoparticles in PP. It is because Silica sand (SiO2) is denser than PP and causes an enhancement of density of PP when added as reinforcement. The densities of PP based SiO2 are given in Table 2.
Table 2: Density measurement for PP composites with different wt% of SiO2 Composites/Density 1st reading 2nd reading Average (g/cm3) (g/cm3) (g/cm3) Pure PP 5% Silica Sand+PP 10% Silica Sand+PP 15% Silica Sand+PP 20% Silica Sand+PP 0.892 0.873 0.883 0.932 0.959 0.852 0.855 0.899 0.876 1.006 0.872 0.864 0.891 0.904 0.983

Fig. 3: Density analysis of PP-SiO2 composites

further analysis by using Field Emission Scanning Electron Microscope (FESEM). Some of the white zones in SEM analysis show that large portion of the polymer matrix is surrounded by the silica sand nanoparticles cause plastic deformation and cohesive failure of the composites. In case of 5wt% less agglomeration take place and fracture areas are not deeper as compared to 20wt% of silica sand nanoparticles, where the fracture areas are deeper and small due to large agglomeration of the nanoparticles (Fig. 8). This was due to non homogeneous mixing and agglomeration between PP and Silica sand nanoparticles thus decrease the tensile strength and result in brittle fracture.
Fig. 4: Fracture Tensile test samples of PP-SiO2 composites

(a)

(b)

Fig. 5: Tensile strength of PP-SiO2 composites

(c) (d) Fig. 8: Fracture surface analysis of PP-SiO2 nanoparticles composites with (a) 5wt% (b) 10wt% (c) 15wt% (d) 20wt% SiO2

IV. CONCLUSION
Fig. 6: Young modulus of PP-SiO2 composites

Fig. 7: Flexural Strength of PP-SiO2 composites

D. SEM analysis of fracture surfaces of Tensile samples of PP-SiO2 composites The fracture surface of 5, 10, 15 and 20 wt% of PP-SiO2 composites tensile samples were observed under SEM for

Based on the above results and discussions, the following statements can be drawn. 1. The addition of silica sand nanoparticles to PP causes an enhancement in physical properties: density from 0.872g/cm3 to 0.983g/cm3. 2. The results of tensile tests indicated that the addition of silica sand nanoparticles decreased the tensile strength with increasing trend of silica sand nanoparticles. In this project, although pure PP recorded the highest tensile strength value, common experimental trend in polymer nanocomposites can be observed from 5% to 20% particle addition. 3. Flexural strength increase when silica sand nanoparticles were added into the PP matrix. PP matrix with 20% addition of nanosilica could be proposed as the optimum mixture ratio. The further analysis can be done to get better understanding about the study. Other properties such as thermal properties can be considered in the future to develop the study.

V. ACKNOWLEDGEMENT The authors would like to express their appreciation to Universiti Teknologi PETRONAS for providing necessary supports and technical assistance in completing this study. REFERENCES
[1] Polymer Degradation, Classle, date accessed: 19 June 2011, 1258am <http://www.classle.net/bookpage/polymer-degradation> [2] Chu Lie Wu, Ming Qiu Zhang, Min Zhi Rong, Klaus Friedrich, Silica nanoparticles filled polypropylene, effects of particle surface treatment, matrix ductility and particle species on mechanical performance of the composites, Composites Science and Technology 65 (2005) 635-645 [3] Chu Lie Wu, Ming Qiu Zhang, Min Zhi Rong, Klaus Friedrich, Tensile performance improvement of low nanoparticles filled-polypropylene composites, Composites Science and Technology 62 (2002) 13271340.

[4] Chaganti Srinivasa Reddy, Chapal Kumar, Das, PolypropyleneNanosilica-Filled Composites: Effects of Epoxy-Resin-Grafted Nanosilica on Structural, Thermal, and Dynamic Mechanical Properties, Journal of Applied Polymer Science, Vol. 102, 2117-2124 (2006) [5] Yiqun Liu, Marianna Kontopoulou, The structure and physical properties of polypropylene and thermoplastic olefin nanocomposites containing nanosilica, Polymer 47 (2006) 7731-7739 [6] R. H. J. Hannink and A. J. Hill (Editor), Nanostructure Control of Materials,Wood head Publishing and Maney Publishing on behalf of The Institute of Materials, Minerals & Mining CRC Press 2006 Boca Raton Boston New York Washington [7] T. Ahmad, O Mamat, Characterization and Properties of Zirconia-Silica Sand Nanoparticles Composites, WJNSE 2011; 1: 7-14. [8] T. Ahmad, O Mamat, Characterization and Properties of Iron-Silica Sand Nanoparticles Composites, DDF 2011; 316-317: 97-106.