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Summary: Several rubber/starch composites in which the starch particles are in an amorphous state and are smaller than 1 mm, prepared by directly mixing and co-coagulating rubber latex and starch paste, exhibit higher hardness, stress at 100%, tensile strength, and tear strength relative to the corresponding rubber/starch composites prepared by direct blending.

TEM micrograph of starch/SBR composite.

Preparation, Structure, and Properties of Starch/Rubber Composites Prepared by Co-Coagulating Rubber Latex and Starch Paste
You-Ping Wu, Mei-Qin Ji, Qing Qi, Yi-Qing Wang, Li-Qun Zhang*
The Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029, China Fax: (86) 10 64433964; E-mail: zhangliqunghp@yahoo.com

Received: September 22, 2003; Revised: November 23, 2003; Accepted: November 24, 2003; DOI: 10.1002/marc.200300125 Keywords: amorphous; co-coagulating; composites; rubber; starch

Introduction
Rubber composites used for the tread of green tires have attracted increasing interest in recent years. This is mainly due to the fact that energy consumption and carbon dioxide emission from automobiles have become a serious threat to the environment. Starch, which is a natural, cheap, and easily biodegradable polymer, has been tentatively used as a tire additive, and a number of achievements have been made.[14] Goodyear Tire Co., for example, uses a new starch-based material called BioTRED to partially replace the conventional carbon black and silica in order to reduce tire weight and rolling resistance, and simultaneously decrease the energy consumption in the production processes. In addition, the new tires, with lighter weight and lower rolling resistance, are expected to reduce fuel consumption and noise. The Goodyear GT3 is claimed to be
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the rst tire on the market using BioTRED, and Ford of Europe expects to use the GT3 on its fuel-economic version of the Ford Fiesta. The mechanical properties of starch-lled rubbers actually depend on many factors, among which the most important ones are the dispersion level, the interfacial strength, and the type of starch. However, the polar surface, high melting point, and large particle size of starch make it difcult to nely disperse starch in a rubber matrix. Therefore, incorporation of starch into rubber by direct blending results in a micro-composite with large, dispersed particles, which causes signicant deterioration of the mechanical properties of vulcanizates, especially the resistance to abrasion and the tear properties.[2] In order to nely disperse starch in a rubber matrix, Buchanan et al.[58] prepared crosslinked starch xanthide-rubber master batches in the 1970s by co-precipitating mixtures
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DOI: 10.1002/marc.200300125

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of soluble starch xanthide and elastomer lattices, during which starch xanthide was crosslinked. In the prepared curds, starch worked as the continuous phase and the latex particles as the disperse phase. The starch-elastomer crumb was further extruded to produce a phase inversion. As a consequence, it was demonstrated that crosslinked starch xanthide could be used as an effective rubberreinforcing agent, especially in improving the fatigue life and abrasion resistance, when used to partially replace carbon black in a premium tread. Recently, a composite of starch/plasticizer with a lower softening point than that of starch was used to blend with rubber at a processing temperature high enough to cause starch to melt, for example in the range of about 150 8C to 170 8C, to generate a ne dispersion of starch in the rubber matrix.[24] However, if this method is applied, it must be carried out at quite a high temperature and may cause the unsaturated elastomers to degrade; additionally, some kinds of plasticizers, such as ethylene vinyl copolymer or poly(vinyl alcohol), which are incompatible with non-polar rubber molecules, are inevitably introduced into the rubber matrix. Another disadvantage of this method is that it is too complex. Carvalho et al.[9] have prepared thermoplastic starch/natural rubber blends, where rubber was the dispersed phase, by mixing a small amount of natural rubber latex with glycerol-plasticized cornstarch in a Haake Mixer without a co-coagulation process. The methods used to nely disperse starch in a rubber matrix and the phase morphology, together with the properties of the produced composites, are very interesting; moreover, they are also important for the application of starch in the rubber industry. In this report, we present a novel dispersion technique developed by our laboratory:[10] compounding rubber latex with natural starch paste and directly co-coagulating the mixture using an electrolyte without crosslinking starch. This strategy originated from the fact that water is a very good chemical medium to dissociate the hydrogen bond in starch, and most rubbers have a latex form. In an aqueous system, the rubber latex particles, which are generally smaller than 100 nm, can be mixed with starch paste uniformly, giving starch/rubber composites with a ne dispersion. Several starch/rubber composites, such as starch/styrene butadiene rubber (SBR), starch/natural rubber (NR), starch/acrylonitrile butadiene rubber (NBR), and starch/carboxylated acrylonitrile butadiene (CNBR) were prepared, and their structure and properties investigated.

Lanzhou Petrochemical Company (China); CNBR latex (AN 3135%) was purchased from Taiwan Nancar Corp.; corn starch (100% amylopectin, 12 wt.-% moisture content) was from Changchun Dacheng Special Corn-Modied Starch Development Co. Ltd (China).

Preparation of Starch/Rubber Composites About 5% starch aqueous suspension was stirred at 90 8C in a water bath for 1 h until the solution became transparent. When the solution cooled to ambient temperature, a starch paste was obtained. Starch paste and the rubber latex were mixed and stirred vigorously for 0.5 h, and then about 2 wt.-% calcium chloride aqueous solution was added to co-coagulate the rubber latex and starch paste. The coagulum was then washed several times with water and dried in an oven at 80 8C for 18 h to a moisture content of about 10%. The starch/rubber blend was then prepared. Starch/rubber blends of the control samples were prepared by directly blending natural starch powder (12 wt.-% moisture content) with SBR, NR, NBR, or CNBR rubber on a two-roll mill at 5060 8C. The vulcanizing ingredients and other additives were mixed into the starch/rubber blends with a two-roll mill at 5060 8C by a standard procedure; the compositions are shown in Table 1. The compounds were vulcanized for t90 at 145 8C for the NR system, 150 8C for the SBR system, and 160 8C for the NBR and CNBR systems. The vulcanized starch/rubber compounds are referred as to the starch/rubber composites.

Characterization X-ray diffraction (XRD) analyses were carried out on a Rigaku D/Max-III C using a Cu target, 40 kV, 200 mA and 6.008 at 2y/ min. Scanning Electron Microscopy (SEM) morphologies were taken from the tensile fracture surface of composites using an S-250-III SEM. Transmission Electron Microscopy (TEM) observations were performed with an H-800 TEM at an acceleration voltage of 200 kV.

Table 1. Compositions of starch/rubber composites (phr/100 phr rubber). Components Starch Zinc oxide Stearic acid Accelerator DM Accelerator CZ Accelerator TT Accelerator D DCP Sulfur Antioxidant 4010NA Antioxidant RD SBR 10 3 1 1.2 0.2 0.5 4 1.8 1 1 2 1 1.5 2 NR 10 5 2 0.5 NBR 10 5 1 1 CNBR 10

Experimental Part
Materials SBR latex (St 23%), was received from Qilu Petrochemical Company (China); NR latex was provided by Beijing Latex Factory (China); NBR latex (AN 2426%) was supplied by
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Mechanical Tests Mechanical tests were performed according to GB (Chinese standard).

Results and Discussion

Morphology
The XRD patterns of starch, pure SBR, and starch/SBR blends containing 50 phr starch, prepared by different methods, are presented in Figure 1. To avoid the overlap of the peak of pure SBR, we obtained the XRD patterns of starch in different starch/SBR blends by subtracting the XRD pattern of pure SBR from the XRD pattern of the starch/SBR blend, as shown in Figure 2. The starch is a semi-crystalline material, and Figure 1a shows the ve diffraction peaks of starch appearing at 14.88, 17.08, 17.98, 19.98, and 22.78, respectively, corresponding to the crystalline region of A-type starch.[11] The XRD pattern of starch in the starch/SBR blend prepared by co-coagulation is presented in Figure 2c. A broad amorphous hill is clearly observed, demonstrating that the starch dispersed in the SBR matrix is in an amorphous state. Once the crystals of starch in the diluted starch paste had disappeared, the starch did not re-crystallize again during the process of mixing and co-coagulating the starch paste with the rubber latex, and not even during the drying process, whereas the blend prepared by direct blending showed peaks at the same 2y values as starch, although with somewhat lower intensity due to the lower starch content of the blend relative to that of the pure starch sample. In the case of starch/NBR blends with 20 phr starch, the XRD patterns of the starch showed the same peaks as those in the starch/SBR blends described in detail above, therefore the results are not presented here.

Figure 2. X-ray diffraction patterns of starch in different starch/ SBR blends: (a) pure starch; (b) starch in starch/SBR blend prepared by direct blending; (c) starch in starch/SBR blend prepared by co-coagulation.

Figure 1. X-ray diffraction patterns of starch and starch/SBR blends containing 50 phr starch: (a) pure starch; (b) pure SBR; (c) starch/SBR blend prepared by direct blending; (d) starch/SBR blend prepared by co-coagulation.
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The starch in the starch/rubber blends prepared by cocoagulation did not show any crystalline peak. It is assumed that the starch dispersed at the molecular level in the rubber matrix and/or the ne gelatinized starch granules probably cause this result.[12,13] In order to further make sure of the starch dispersion, we observed the tensile fracture surfaces of starch/rubber composites prepared by the two different methods by SEM. SEM micrographs of starch particles, starch/SBR and starch/NBR composites prepared by co-coagulation or direct blending are shown in Figure 3. The size of the starch particles in the starch/rubber composites prepared by direct blending (Figure 3b and 3d) remains almost the same as that of the original starch, i.e. about 520 mm (Figure 3a). This result is consistent with the XRD patterns (Figure 2a and 2b) and reects the fact that the shearing force exerted by the two-roll mill during blending is not high enough to break the starch particles, due to the large number of hydrogen bonds and high cohesion energy. In addition, some apparent holes with the same size as the starch particles are left on the fracture surface of the composites (Figure 3b and 3d), which strongly suggests that the interfacial interaction between the starch and rubber is very weak. In Figure 3c, it can be seen that the fracture surface of the starch/SBR composite prepared by co-coagulation is very smooth and the light areas of starch granules are smaller than 5 mm. This sample did not exhibit crystalline peaks in the XRD pattern (Figure 2c). The fracture surface of the starch/NBR composite prepared by co-coagulation (Figure 3e) is coarse, maybe due to the polarity of NBR; the size of the starch granules is also smaller than 5 mm. The gelatinized starch granules prior to co-coagulation did not re-crystallize during the process of drying; this crystallization behavior needs to be investigated further. The dispersion of starch particles in the starch/NR and starch/CNBR composites prepared by the two different methods exhibits a similar
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Figure 3. SEM micrographs of starch particles and the tensile fracture surface of starch/rubber composites: (a) starch particles; (b) starch/SBR composite prepared by direct blending; (c) starch/SBR composite prepared by co-coagulation; (d) starch/NBR composite prepared by direct blending; (e) starch/NBR composite prepared by co-coagulation.

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trend to that in the starch/SBR and starch/NBR composites, therefore the SEM photographs are not shown here. Since SEM could not give us any detailed information about the starch granules in Figure 3c and 3e, we also conducted TEM observations of the starch/SBR and starch/NBR composites. TEM micrographs of starch/SBR and starch/NBR composites are shown in Figure 4. The light areas of the photographs are the holes left by starch granules removed during the process of cutting samples by ultramicrotomer at liquid nitrogen temperature; the starch granules are smaller than 1 mm. SEM and TEM both strongly demonstrate that our method of directly co-coagulating starch paste and rubber latex to prepare the starch/rubber composites is applicable to rubbers with latex to get a ne dispersion of starch in the rubber matrix.

The Mechanical Properties of Starch/Rubber Composites

The mechanical properties of the gum vulcanizates and starch/rubber composites prepared by co-coagulation or direct blending are presented in Table 2. In contrast to starch/SBR, starch/NR, starch/NBR and starch/CNBR composites prepared by direct blending, the corresponding composites prepared by co-coagulation exhibit higher hardness, stress at 100%, tensile strengths, and tear strengths. This difference is assumed to result from the ne dispersion of the starch in these rubber/starch composites. The increase in mechanical properties of the NBR/starch composite is larger than that of the SBR/starch composite, possibly due to the polarity of NBR.
Figure 4. TEM micrographs of starch/rubber composites: (a) starch/SBR; (b) starch/NBR.

Conclusion
The crystalline nature of starch was reduced and sometimes even disappeared in starch/rubber compounds produced
Table 2.

Mechanical properties of starch/rubber composites with 10 phr starch. Shore A hardness Stress at 100% MPa Tensile strength MPa 2.3 2.6 3.6 23.7 19.1 26.8 3.2 4.0 7.3 5.7 5.7 7.8 Elongation at break % 524 480 544 720 748 708 308 332 308 208 256 200 Permanent set % 8 4 4 24 12 28 4 2 4 0 2 4 Tear strength kN/m 12.1 14.0 19.9 31.2 23.0 35.5 14.3 15.2 24.3 18.9 12.7 35.1

Pure SBR Starch/SBR by direct blending Starch/SBR by co-coagulation Pure NR Starch/NR direct blending Starch/NR by co-coagulation Pure NBR Starch/NBR direct blending Starch/NBR by co-coagulation Pure CNBR Starch/CNBR direct blending Starch/CNBR by co-coagulation
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44 50 50 38 40 41 54 56 68 67 75 78

0.8 0.8 1.1 0.5 0.7 0.7 1.2 1.3 2.5 2.2 1.6 4.3
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by co-coagulation, and the size of the starch particles decreased dramatically; more specically, to smaller than 1 mm. This caused a large improvement in the mechanical properties of the starch/rubber composites. This technique of compounding starch paste and rubber latex is a new, promising way to prepare rubber/starch composites and is suitable for rubbers with a latex form.

Acknowledgement: This work was supported by the Youth Natural Science Foundation of Beijing University of Chemical Technology (No. QN0302).

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[3] USP 6 273 163 (2001), The Goodyear Tire & Rubber Company, invs.: T. F. E. Materne, F. G. Corvasce; Chem. Abstr. 2001, 135, 305039r. [4] USP 5 672 639 (1997), The Goodyear Tire & Rubber Company, invs.: F. G. Corvasce, T. D. Linster, G. Thielen; Chem. Abstr. 1997, 127, 249241w. [5] R. A. Buchanan, W. F. Kwolek, H. C. Katz, C. R. Russell, rke 1971, 23, 350. Starch/Sta [6] R. A. Buchanan, H. C. Katz, C. R. Russell, C. E. Rist, Rubber J. 1971, 153, 28. rke 1974, 26, 165. [7] R. A. Buchanan, Starch/Sta [8] R. A. Buchanan, W. M. Doane, C. R. Russell, W. F. Kwolek, J. Elastomers Plast. 1975, 7, 95. [9] A. J. F. Carvalho, A. E. Job, N. Alves, A. A. S. Curvelo, A. Gandini, Carbohydr. Polym. 2003, 53, 95. [10] CN 03100424.5 (2003), Beijing University of Chemical Technology, invs.: L. Q. Zhang, M. Q. Ji, Y. P. Wu. [11] O. N. Campas-Baypoli, E. C. Rosas-Burgos, P. I. Torres vez, B. Ram rez-Wong, S. O. Serna-Sald var, Starch/ Cha rke 2002, 54, 358. Sta rke 2000, [12] X. Z. Han, B. R. Hamaker, W. Lafayette, Starch/Sta 52, 76. [13] D. H. S. Ramkumar, M. Bhattacharya, J. Mater. Sci. 1997, 32, 2565.

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