Materials Letters 62 (2008) 43964399

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Microcellular foams of thermoplastic vulcanizates (TPVs) based on waste ground rubber tire powder
Zhen Xiu Zhang a, Shu Ling Zhang a,b, Sung Hyo Lee a, Dong Jin Kang c, DaeSuk Bang c, Jin Kuk Kim a,
a b c

School of Nano and Advanced Materials Engineering, Gyeongsang National University, Jinju, 660-701, South Korea Alan G. MacDiarmid Lab, College of Chemistry, Jilin University, Changchun, 130012, People's Republic of China Department of Polymer Engineering and Science, Kumoh National Institute of Technology, Gyungbuk, 730-701, South Korea

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With the increased adoption of thermoplastic vulcanizates (TPVs) in automotive weather seal systems, the foams of TPVs present an important milestone in providing key applications such as trunk and door seals. In this study, microcellular foams of TPV based on waste ground rubber tire powder (WGRT) were investigated. In order to investigate the relationship between processing conditions and structure of TPV foams, we rst prepared the thermoplastic vulcanizates of PP-g-MA/WGRT, then the samples were saturated with carbon dioxide and the saturated specimens were expanded during the pressure-quench process. The results indicated that the microcellular structure was dependent on the processing conditions. Cell size increased with saturation temperature, whereas cell density and relative density decreased. Different nucleation processes were produced with saturation pressure. Crown Copyright 2008 Published by Elsevier B.V. All rights reserved.

Article history: Received 1 October 2007 Accepted 24 July 2008 Available online 26 July 2008 Keywords: Foam Thermoplastic vulcanizates Waste ground rubber tire powder Microstructure

1. Introduction To date the best choice for automotive weather seal materials is ethylenepropylene diamine monomer (EPDM) rubbers [1]. Over the last decade, thermoplastic vulcanizates have gained increasing acceptance in numerous elds as a replacement for thermoset rubber due to its rubber-like performance coupled with the ease of processing associated with thermoplastics. Despite these advantages compared to thermoset EPDM, the lack of foaming technology for TPVs has limited their use. In order to solve the acute problem of waste ground rubber tires, our lab is researching the thermoplastic vulcanizates from WGRT [2]. The aim of the work is to prepare the microcellular foams based on thermoplastic vulcanizates of PP-g-MA/WGRT and discuss the inuence of processing conditions on the structure of the foams. By providing a closed cell structure, microcellular foams of PP-g-MA/WGRT offer an opportunity to incorporate the advantage of TPVs into foam materials, which enlarges their application elds.

2. Experimental 2.1. Materials and sample preparation Polypropylene (R520Y) was manufactured by SK Corporation. Maleic anhydride (MA) and dicumyl peroxide (DCP) were reagent grade and obtained commercially from Aldrich. Maleic anhydridegrafted polypropylene (PP-g-MA) was prepared by our lab according to the earlier literature [3]. The particle size of waste ground rubber tire powder was 50 meshes. CO2 with a purity of 99.95% was supplied by Hyundai Gas Inc. Blends of PP-g-MA/WGRT (50/50) were extruded in a twin-screw extruder at the screw speed of 120 rpm and temperature prole of 130/150/160/160/180/180/180/180/190 C. The resulting blends were molded at temperature proles of 190/200/210/ 220 C by injection.

Table 1 Processing conditions and foam characteristics for PP-g-MA/WGRT (50/50) samples Pressure MPa 16 16 16 16 10 12 14 18 Temperature C 140 145 150 154 150 150 150 150 Average cell size D m 31 75 86 25 149 191 51 Cell density N0 cells/cm3 1.77 108 8.41 107 7.56 107 2.85 108 6.21 106 5.41 106 1.98 108 Relative density % 0.6080 0.4187 0.0989 0.0752 0.4685 0.1610 0.0952 0.1294

Corresponding author. Tel.: +82 55 751 5299; fax: +82 55 753 6311. E-mail address: rubber@gsnu.ac.kr (J.K. Kim).

0167-577X/$ see front matter. Crown Copyright 2008 Published by Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2008.07.039

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scope (SEM). The cell diameter (D) is the average of all the cells on the SEM photo, usually more than 100 cells were measured. D d==4 1

Where d is the measured average diameter in the micrograph. The density of foam and unfoamed samples was determined from the sample weight in air and water respectively, according to ASTM D 792 method A. Then the density of the foamed sample is divided by the density of the unfoamed sample to obtain the relative density (r). The volume fraction occupied by the microvoids (Vf) was calculated as
Fig. 1. Microstructure of PP-g-MA/WGRT foam (scale bar is 50 m).

Vf 1

f m

2.2. Foam preparation The foams were prepared with a pressure-quench method described by Goel and Beckman [4]. Plate samples (2 3 12 mm) were enclosed high-pressure vessel. The vessel was ushed with lowpressure CO2 for 3 min and preheated to desired temperature. Afterward, the pressure was increased to the desired pressure by a high-pressure pump and maintained at this pressure for 1 h. After saturation, the pressure was quenched to atmospheric pressure within 3 s and the samples were taken out. Then foam structure was allowed to full growth during rapid depressurization. The processing condition is listed in Table 1. 2.3. Foam characterization The foamed samples were fractured in liquid nitrogen, coated with an approximately 10-nm thick layer of gold on the fractured surface, and observed with a Philips XL 30-S-FEG scanning electron micro-

Where m and f are the density of the unfoamed polymer and foamed polymer respectively. The cell density (N0) based on the unfoamed sample was calculated as V Nf f 3 6D N0 Nf 1Vf 3

Where Vf is the volume fraction occupied by the microvoids, Nf is the cell density based on the foamed sample.
3. Results and discussion 3.1. Mechanical properties and microstructure of thermoplastic vulcanizates of PP-g-MA/ WGRT Thermoplastic vulcanizate (TPV) is a special class of thermoplastic elastomers (TPEs) made of a rubber/plastic polymer mixture in which the rubber phase is highly vulcanized. One of major criteria for a thermoplastic vulcanizate is that elongation at

Fig. 2. SEM micrographs of the specimens produced at different saturation temperature (a) 140 C, (b) 145 C, (c) 150 C, (d) 154 C. (Scale bar is 50 m).

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Fig. 3. SEM micrographs of the specimens produced at different saturation pressure (a) 10 MPa, (b) 14 MPa, (c) 16 MPa, (d) 18 MPa. (Scale bar is 200 m).

break is more than 100%. For PP/WGRT (50/50) blend, tensile strength is 11.5 MPa and elongation is only 39.4%. In order to obtain TPV based on WGRT, PP is replaced by PP-gMA. The reactivity of MA group in PP-g-MA and phenolic OH group in WGRT can enhance the compatibility between PP and WGRT [2]. The result is that tensile strength is 11.9 MPa and elongation is 210.4% for PP-g-MA/WGRT (50/50) blend, namely we have successfully prepared TPV based on WGRT. Fig. 1 shows a typical microstructure of PP-gMA/WGRT foam. The specic feature of this structure is a microcellular matrix and an expanded interphase between matrix and WGRT powder. 3.2. Inuence of saturation temperature on the microstructure of PP-g-MA/WGRT foam It has been reported saturation temperature is an important processing parameter to control the foam structure of microcellular polymer [58]. Fig. 2 shows foam structures of PP-g-MA/WGRT (50/50) blend obtained at different saturation temperature for a given saturation pressure of 16 MPa, saturation time of 1 h and depressurization time of 3 s, and foam characteristics for PP-g-MA/WGRT (50/50) blend can be seen in Table 1. From Table 1, it can be found that the average cell size increases with saturation temperature, whereas the cell density and relative density decrease. For PP-g-MA/WGRT (50/50) blend, the cell density and relative density at 140 C are not included in Table 1 due to very inhomogeneous microstructure. As saturation temperature increases, the expansion increases and the cell walls become thinner and a structure with a polygonal cells is developed. When the saturation temperature increases, the crystalline phase could be partly or totally disrupted. Thus CO2 is expected to be dissolved in and diffuse through both the amorphous phase and the disrupted part of the crystalline phase [9]. Thus conditions become more favorable for PP-g-MA/WGRT (50/50) blend to foam and for the cells to grow bigger in size. Accordingly, cell density and relative density decrease. 3.3. Inuence of saturation pressure on the microstructure of PP-g-MA/WGRT foam Fig. 3 shows foam structures of PP-g-MA/WGRT (50/50) blend obtained at different saturation pressure for a given saturation temperature of 150 C, saturation time of 1 h and depressurization time of 3 s, and foam characteristics for PP-g-MA/WGRT (50/50) blend can be seen in Table 1. From Table 1, it can be found that the average cell size rst increases with saturation pressure until 14 MPa and decreases from 14 MPa to 18 MPa. Accordingly, the cell density and relative density rst decrease with saturation pressure until 14 MPa and increase from 14 MPa to 18 MPa. The increase of saturation pressure usually brings about two effects on the cell growth. On the one hand, when the saturation pressure increases, the extent of the CO2 induced-melting temperature depression increases, namely the amount of CO2 dissolved in samples increases. Thus sample is relatively soft and its deformability and foamability are large. The result is that increasing saturation pressure becomes

more favorable for sample to foam and for the cells to grow bigger in size. On the other hand, when the saturation pressure increases, namely depressurization rate increases due to the same depressurization time, the cells have no enough time to grow bigger in size. As the saturation pressure is lower, both the CO2 induced-melting temperature depression and the amount of CO2 dissolved in sample become very important, so the average cell size rst increases with saturation pressure until 14 MPa, whereas the corresponding cell density and relative density rst decrease. As the saturation pressure is higher, the effect of depressurization rate on cell growth becomes very obvious, so the average cell size decreases with saturation pressure from 14 MPa to 18 MPa whereas the corresponding cell density and relative density increase.

4. Conclusion By maleic anhydride-grafted polypropylene (PP-g-MA) replacing polypropylene (PP), we successfully prepare thermoplastic vulcanizate (TPV) based on waste ground rubber tire powder (WGRT) due to the enhanced compatibility between PP and WGRT. The enhanced compatibility results from the reactivity of MA group in PP-g-MA and phenolic OH group in WGRT. The effects of processing conditions on the structure of PP-g-MA/WGRT foams were investigated. Higher saturation temperature resulted in larger cell size, lower cell density and relative density, whereas different nucleation processes were produced with the increase of saturation pressure. Namely the average cell size rst increases then decreases with saturation pressure, whereas the cell density and relative density rst decrease then increase. In a word, the abundance of foaming technology for TPV based on WGRT enlarges their application elds. Acknowledgement The authors are grateful to the support from the BK21 program in South Korea. References
[1] Harper CA. Handbook of Plastics, Elastomers and Composites. 3rd edition. New York: McGraw-Hill; 1996. p. 5. 21.

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