Study on Kneading and Molding of PP /TiO2 Nanocomposite

Study on Kneading and Molding of PP /TiO2 Nanocomposite

C. K. Huang Xin-Yi Li

Department of Mechanical Engineering, Lunghwa University of Science and Technology ABSTRACT

This paper investigates the kneading and molding of PP (polypropylene) with nano-TiO2 (Titanium dioxide) powder having sizes in the range of 50 nm. It is found that; quality feedstock with uniform nanopowder dispersion was achieved only when the kneading was performed for optimum time under optimum torque using a custom-made triple-screw kneader with a high shear force. The torque and kneading time needed for PP composite with 40wt% nano-TiO2 is double than that required for the one with 10wt%. The wear abrasion of composites with 10wt% and 40wt%, filler loading was also tested. In addition, a very important result revealed that a simple micro-grating can be successfully used as a mold insert to replicate microfeatures made with PP/nano-TiO2 feedstock using the injection molding conducted in a high forming pressure, a high mold temperature, and evacuation of the mold.

Key words: Kneading, injection molding, nanocomposite, dispersion, microfeature 1. INTRODUCTION

A number of pure plastics have been successfully fabricated through injection molding [1-4]. However, most of them, such as microgears and microfans, require high strength and wear resistance. Only plastic materials cannot satisfy these requirements. Some researchers [5-10] have successfully produced microparts by the addition of reinforced fillers through microinjection molding. The results revealed that the microparts could be strengthened by adding nano-materials. PP polymer is one of the most widely used in the industrial field. PP can be easily modified with blending inorganic fillers in order to obtain higher mechanical properties. PP composites find applications as microgears and the computer housing for
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electronic applications. In the meantime, TiO2 is found to be significantly harder material used to fabricate nanowires and nanotips. In addition, TiO2 nanoparticles have been used as a photocatalyst. For example, it can be coated on many building materials. The coated films exhibit a self cleaning effect due to the strong oxidizing properties. Photocatalytic activity in TiO2 has been extensively studied because of its potential use in sterilization, sanitation, and remediation applications. Thus, PP with added reinforcing TiO2 nanoparticles will be an interesting combination. However, it is difficult to disperse nanoparticles uniformly in the polymer compound through traditional kneading processes. Song et al. [11] showed their control in kneading process to manufacture

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various zirconia feedstocks. The powder agglomeration in the feedstock is due to the insufficient shear stress provided by the kneader. Wu and Wei [12-13] conducted the measurements on torque versus time variation as functions of the temperature and the kneading speed. The agglomerated micro-powders were shear-kneaded by twin-screw kneader and uniformly dispersed in the binder. It has been established that the organic nature of nanoparticle surfaces is a key factor to promote the dispersion of the nanoparticles in the matrix [14-17]. These results revealed that the composite feedstocks will have good quality only in the presence of dispersive agents and the kneading shear force must be high enough. The author [18] has been researched the kneading of the polymer with 20wt% added nano-ZnO particles using the twin-screw kneader. The results, similar to the previous researchers, showed that some of nanofillers were agglomerated in the polymer due to insufficient shear force during kneading. Thus, triple-screw kneader with three contact surfaces to provide a strong shear force to disperse nanoparticles among the polymer is explored in this study. In addition, one simple micro-grating used as a mold insert to replicate microfeatures made with PP/nano-TiO2 feedstocks using the injection molding will be studied in this research.

materials supplied by Z-tech Co., USA, with diameter of 50 nm were used as fillers to reinforce the mechanical properties of parts. The TiO2 particles, as shown in Fig. 1, were heavily agglomerated. They were needed to be dispersed by high shear force. Polypropylene (PP, Formosa Plastic, Taiwan) was used as the polymer matrix. Stearic acid (SA, Nacalai Tesque, Japan), FP1 (ICI, England), and their combination were used as dispersion agents. Both surfactants were popular used in the market. Optimum dispersant was then chosen after sedimentation experiments were conducted. The weight content of TiO2 particles in the polymer matrix was 10% and 40%, respectively. The required amounts of dispersion agent (0.5% to 2%) were added to the kneader during mixing of PP and TiO2. 2.2 Sedimentation and kneading processes The suspensions for sedimentation experiments were prepared by mixing 54 ml heptane with a specified surfactant and 1.5 g TiO2 particles. The sedimentation height ratio of Hf (Final height) and Ho (Original height) was measured after 7 days. The dispersive effect is better when Hf/Ho is smaller. A custom-made triple-screw kneader with high shear force, as shown in Fig. 2, was used to mix reinforcing powders with the polymer. This machine mainly includes power, torque, and kneading units. The power of machine is supplied by an electric motor of 1 hp. The torque can be produced through torque transducer when power is driving. The torque will actuate the triple screws to knead feedstock through connect.
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2. Experimental Procedure
2.1 Materials The raw materials used in the study included TiO2 particles, PP, and surfactant. The TiO2 particles which were commercial

Study on Kneading and Molding of PP /TiO2 Nanocomposite

The kneading unit mainly includes triple screws with diameter of 40 mm and a heater. At first TiO2 powders are fed in to the chamfer to granule using triple screws first. Then, the polymer and surfactant are added into the chamfer to blend with nanopowders into a feedstock. The pitch of screws with 30 and 150 degrees with horizontal axis is used to provide shear force to blend feedstock. Twin-screw kneader was usually used to blend micropowders with a polymer, as shown in Fig. 3(a). The twin-screw kneader is easy to blend micropowders with polymer feedstock [12-13]. However, the polymer/nanoparticle composite cannot be blended well. Thus, triple-screw kneader with three contact surfaces, as shown in Fig. 3(b), is needed to produce higher shear force to blend a uniform nanocomposite. At the beginning of the kneading process, pure TiO2 nanoparticle with 10% and 40%, respectively, of the total weight content of the polymer compound were preheated to 170oC in the kneader. PP plastic pellets and surfactant were then added to the powders and kept at 180oC in the kneader. Amount of surfactant as required was added into the mixture until the uniform feedstock was produced. 2.3 Wear and molding tests for PP/TiO2 nanocomposite A wear test was used to estimate the quality of composites with added reinforced nanoparticles. Wear test was carried out by using a pin-on-disk tester (Micro phonics, USA). Cylindrical specimens with a diameter of 8 mm and a thickness of 10 mm were used in wear tests, as per ASTM G99-04. Round specimen was placed in
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contact with the disk which had a surface roughness of 0.2 m(Ra) at a position 37 mm from the center and rotated from 2,500 (0.58km) to 30,000 revolutions (6.97km) with a step increase of 2,500 revolutions at a constant speed of 70 rpm. The vertical load on the pin was 5 kgf. Then, the weight of each specimen was measured using an electronic weighing machine (Honeywell, UK). The weight loss ( wl ) was then calculated as follows:
wl =

w w 100% w

Where w is the weight before wearing and w is the residual weight after wearing test. To achieve high quality, low weight loss is required. The silicon square-shaped grating with a height of 0.9 m and a width of 1.1 m provided 3 m-pitch pillars with slightly extended linear edges, as shown in Fig. 4. The grating with microfeatures was used in this study to investigate the moldability of polymer with added nanoceramic material. Grating, made by the NT-MDT Co., Russia, was used to calibrate the precision of the AFM (Atomic Force Microscope, Veeco CP-II, New York). Here, the grating was used as a mold insert to replicate the microfeatures using injection molding.

3. RESULTS AND DISCUSSION

3.1 Dispersive properties in sedimentation test The sedimentation results of TiO2 nanoparticles with different dispersants are shown in Fig. 5. The sample with FP1 additive exhibited a least sedimentation height. The height ratio (Hf/Ho) of the TiO2

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particles with FP1 decreased by 25% compared to that without surfactant. However, the other two systems, either SA or the combination of FP1 and SA, showed less effective for the dispersion of the nanoparticles in the polymer matrix. Therefore, FP1 surfactant was used in the samples for following tests. From the sedimentation results, the Hf /Ho ratio of the TiO2 sample with FP1 was about 20%, which means the nanoparticle packing is about 20% after the dispersant FP1 is added into the nanocomposite. In other words, these primary nanoparticles could not be 100% dispersed due to strong bonding between particles even effective dispersant FP1 added. Therefore, the triple-screw kneader with high shear force is needed to disperse these 20% agglomerated nanoparticles among polymer and discussed as following.
3.2 Kneading behavior of the feedstock The kneading response of the PP polymer with 10wt% and 40%, respectively, added nanoparticles was measured by a torque rheometer, as shown in Fig. 6. Both composites have the same trend in torque and time relation. The torque needed for PP composite with 40wt% nano-TiO2 is double

than that required for the one with 10wt% nano-TiO2. At the beginning, the torque significantly increased the value when TiO2 nanoparticles were granuled at chamfer about 10 min (stage a-b). Then, the torque is dramatically decreased because PP changes from solid state to molten state whilst mixing with the nanoparticles (stage b-c). Amount of FP1 surfactant as required
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(among 0.5% to 2%) was added into the mixture. The peak is so called loading peak when the PP polymer begins to blend with TiO2 nanoparticles to produce a granule-dough stage. The feedstock then turned into dough stage and produced consistent properties (stage c-d). The torque was in a stable value. A homogeneous feedstock was produced when consistent plastic properties were detected. The kneading time of a homogeneous feedstock with 40wt% added nano-TiO2 also doubled that of a homogeneous feedstock with 10wt% added nano-TiO2. However, over dough in feedstock was produced and the torque also needed to be increased when the feedstock was continued to be blended (stage d-e). In this stage, polymer was degraded when high temperature of 180oC was continued to apply in the mixing feedstock. In other words, homogeneous feedstock can be obtained when the suitable kneading time and torque power are applied in both nanocomposites. OM (Transmission optical microscope) images, as shown in Figs. 7-8(a), show that the agglomerations exist in both the composites when feedstock was in a granule-dough stage. The nanoparticles were dispersed well when the feedstocks were in dough stage for both composites, as shown in Figs. 7-8(b). The nanoparticles were slightly re-agglomerated when feedstock was in over-dough stage, as shown in Figs. 7-8(c). OM images revealed that the nanoparticles dispersed status could be observed in torque-time profile constructed by our custom-made triple-screw kneader. It also proved that the polymer composites

Study on Kneading and Molding of PP /TiO2 Nanocomposite

with 10wt% or even 40wt% added nanoparticles can be homogeneously kneaded in our custom-made triple-screw kneader with high shear force. Next, the feedstock with 10wt% and 40wt%, respectively, added nanoparticles was used to fabricate specimens to conduct the wear tests. Wear loss of polymer with 10wt% and 40wt% added nanoparticles is shown in Fig. 9. The weight loss increased significantly when the specimen made with neat PP polymer. The weight loss steadily increased when the specimens were rotated for both nanocomposites. Wear loss of PP with 10wt% and 40wt%, respectively, added nanoparticles, was decreased by 300% and 500% compared to neat PP. During wearing, the polymer in the compound was stripped, leaving only the nanofillers, which were much harder than the polymer and resisted wear abrasion. After the fillers were worn down, the next layer of polymer compound continued to wear. This clearly shows that adding nanoparticles to the polymer effectively decreased wear abrasion. The greater the powder content, the lower the wear abrasion.
3.3 Replication of microfeatures SEM (Scanning Electron Microscopy, Japan, JSM-6500F) images of a replicated grating made with PP polymer with 10wt% added TiO2 nanoparticles are shown in Fig.

(Glass transition temperature), a frozen layer formed as the molten polymer flowed into the cavity [14-15]. In other words, high pressure was needed to accelerate filling of the cavity with molten polymer before the polymer froze. Square-shaped features were better replicated at a higher injection pressure of 600 bars and a higher mold temperature of 100oC which was higher than the Tg of nanocomposite by 5oC, as shown in Fig. 10(b). However, some square-shaped pillars were not completely filled, and some square-shaped pillars were over-filled. Possible reason is the waste air existed in the mold cavity, resulting in the random formation of square-shaped features although a higher pressure and a higher mold temperature were applied during replicating. Next, the mold was evacuated, and a higher forming pressure of 600 bars and a higher mold temperature of 100oC were applied in the replication of microfeatures. It can be observed from the image that the replicated square-shaped micro-features made with the polymer composite were well formed with clear structural definition, as shown in Fig. 10(c). The square-shaped microfeatures with a height of 0.9 m and a width of 1.1 m were clearly formed. Here, polymer on one edge of each micro square pillar was shifted because the prototype square-shaped grating had an extended edge shown in Fig. 4. The results revealed that a simple and inexpensive micro-grating can be successfully used as a mold insert to replicate microfeatures made with the polymer nanocomposite. High quality
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10. Short-shot was produced in grating, as shown in Fig. 10(a), when a lower injection pressure of 200 bars and a lower mold temperature of 40oC were employed during processing in this case. Roughly square-shaped features were formed. When the mold temperature was lower than the Tg

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microfeatures could be obtained using the injection molding with the optimum processing conditions, including a high forming pressure of 600 bars, a high mold temperature of 100oC, and evacuation of the mold.

4. CONCLUSION
Based on this study on the kneading and molding of PP/nano-TiO2 composites, the following conclusions can be drawn. 1. The sedimentation results of TiO2 particles showed that, FP1 surfactant is more effective for the dispersion of the nanoparticles. However, the nanoparticles tend to agglomerate beyond 20% filler loading even in presence of surfactants. These agglomerated nanoparticles should be dispersed by effective shear force. 2. The torque-time profile for kneading of PP with nano-TiO2 was reported by using triple-screw kneader with high shear force. The homogeneity of the feedstock gradually improved after the FP1 surfactant was added into the mixture. The results revealed that the agglomerated nanoparticles can be dispersed among the polymer using triple-screw kneader. The torque and kneading time needed for PP composite with 40wt% nano-TiO2 is double than that required for the one with 10wt% 3. The weight loss decreased significantly when more nanofillers were added to the polymer compound. Weight loss of PP with 10wt% and 40wt%, respectively, added nanoparticles, was decreased by 300% and 500% compared to neat PP.
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The greater the particle content, the lower the wear abrasion. replicated square-shaped 4. The micro-features made with the nanocomposites were well formed with clear structural definition using injection molding. The results revealed that simple micro-grating was successfully used as a mold insert to replicate microfeatures using the injection molding conducted in a high forming pressure, a high mold temperature, and evacuation of the mold.

References
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Study on Kneading and Molding of PP /TiO2 Nanocomposite

nanomaterials. European Polymer Journal 2006; 42(9):2174-2184. 7. Merz L, Rath S, Piotter V, Ruprecht R. J Ritzhaupt-Kleiss, J Hausselt, Feedstock development for micro powder injection moulding. Microsystem Technologies 2002;8(2):129-132. 8. Gietzelt T, Piotter V, Jacobi O, Ruprecht R, Hausselt J. Fabrication of micromolds for gearwheels by micro powder injection moulding. Advanced Engineering Materials 2003; 5(3):139-145. 9. Chandra A, Turng LS, Gopalan P, Rowell RM, Gong S. Semitransparent poly(styrene-r-maleic anhydride)/alumina nanocomposites for optical applications. Journal of Applied Polymer Science 2007; 105(5):2728-2736. 10. Yuan M, Winardi A, Gong S, Turng LS, Effects of nano- and micro-fillers and processing parameters on injection-molded microcellular composites. Polymer Engineering & Science 2005; 45(6):773-778. 11. Song JH, Evans JRG. The effect of undispersed agglomerates on the relative viscosity of ceramic moulding suspensions. J. Mater. Sci. Lett. 1994;13(22):1642-1644. 12. Wu RY, Wei WCJ. De-agglomeration of feedstocks with granule TZP powder. J. Europ. Ceram. Soc. 2004;24(14):3653-3662. 13. Wu RY, Wei WCJ. Kneading behavior and homogeneity of zirconia feedstocks for micro injection molding. J. Am. Ceram. Soc. 2005;88(7):1734-1739. 14. Zhao H, Li RKY. A study on the
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photo-degradation of zinc oxide (ZnO) filled polypropylene nanocomposites. Polymer 2006;47(9):3207-3217. 15. Ash BJ, Siegel RW, Schadler LS. Mechanical Behavior of Alumina/Poly(methyl methacrylate) Nanocomposites. Macromolecules 2004;37(4):1358-1369. 16. Ngo TD, Ton-That MT, Hoa SV, Cole KC. Reinforcing effect of organoclay in rubbery and glassy epoxy resins, part 1: Dispersion and properties, Journal of Applied Polymer Science 2008;107(2): 1154-1162. 17. Matsumoto A, Ohtsuka K, Kimura H, Adachi SI, Takenaka M. Moldability and properties of phenolic/artificial zeolite composites, Journal of Applied Polymer Science 2007;106(6):3666-3673. 18. Huang CK, Chiu SW. Formability and accuracy of micropolymer compound with added nanomaterials in microinjection molding. Journal of Applied Polymer Science 2005;98(5):1865-1874.

Figure Captions
Fig. 1 SEM image for pure TiO2 nanoparticles in heavily agglomerating. Fig. 2 Custom-made triple-screw kneader with three contact surfaces to produce high shear force (Unit: mm). Fig. 3 Comparison of kneading surfaces for (a) twin screws and (b) triple screws. Fig. 4 SEM image of silicon squared-shaped calibration grating with microfeatures and extended linear edges.

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Fig. 5 Sedimentation results of the TiO2 nanoparticles with different surfactants for 7 days. Fig. 6 Kneading torque-time profile of PP polymer with 10wt% and 40wt% added TiO2 nanoparticles. Fig. 7 Thin film morphologies of PP feedstock with 10wt% added TiO2 by transmission optic microscope for (a) granule-dough, (b) dough, and (c) over dough stages. Fig. 8 Thin film morphologies of PP feedstock with 40wt% added TiO2 by transmission optic microscope for (a) granule-dough, (b) dough, and (c) over dough stages. Fig. 9 Weight loss of wear tests for PP/TiO2 nanocomposites. Fig. 10 SEM images of square-shaped micro-grating made with PP with 10wt% added TiO2 nanocomposite. (a) With a low injection pressure and mold temperature, (b) a high injection pressure and mold temperature, and (c) a high injection pressure and mold temperature with evacuation.

Power Unit

Torque Unit

Kneading Unit

(1)stepless gear-change (2)two-line motor (3)reduction worm gear (4,6,7)connect (5)torque transducers (8)gear wheel (9)ball bearing (10)screw nut (11)screw bolt (12)blend raw material model (13)heater stick (14)prop stand (15)plinth (16)heater

Fig. 2 a
A and B screw C screw
A C B

D-D

Fig. 3

Extended edges Fig. 1

Fig. 4

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Study on Kneading and Molding of PP /TiO2 Nanocomposite

Fig. 5

Fig. 7 a

Fig. 6 a

10m

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c b

10m

Fig. 8

Fig. 9

Fig. 10

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Study on Kneading and Molding of PP /TiO2 Nanocomposite

PP/TiO 2

PP(Polypropylene) 50 /PP 40wt% PP/10wt% PP/

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