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J O U R N A L O F M A T E R I A L S S C I E N C E L E T T E R S 1 8 (1 9 9 9 ) 1457 1459

Percolation effect and mechanical behavior of carbon black lled polyethylene

I. CHODAK, I. KRUPA Polymer Institute, Slovak Academy of Sciences, 842 36 Bratislava, Slovakia

The percolation threshold effect is a well-known phenomenon observed in ller-matrix systems as the extreme change of certain physical properties within a rather narrow concentration range of heterogeneity. Electroconductive composites consisting of an insulating polymeric matrix and an electroconductive ller frequently demonstrate such a behavior [13]. The effect is observed on the dependence of conductivity vs. ller content and manifests itself as a dramatic increase of conductivity by several orders of magnitude in a rather narrow concentration range of the ller around the socalled percolation threshold. The effect is explained by a formation of a conductive path through the sample by such a way that the conductive particles which create the path are in contact at the ller concentration corresponding to the percolation threshold. The most frequently used electroconductive particles used as llers for conductive composites are either nely dispersed metals or various forms of carbon. Among carbon llers, carbon blacks and graphites are the most important and generally applied for materials with various levels of electroconductivity. The percolation concentration of carbon black depends on many parameters such as the physical nature of the ller (e.g. surface area, aggregation, shape), chemical composition of the surface, and the conditions of processing [4]. The factors such as the nature of the matrix, its viscosity as well as temperature of testing plays an important role regarding the electroconductivity of the composite. Several models have been proposed to describe the percolation behavior of electroconductive composites [5], nevertheless, none of them was found to be generally valid. Mechanical properties of polymers are signicantly inuenced by the presence of llers. When mixing thermoplastics with the electroconductive ller, besides an increase of electroconductivity, an increase of Youngs modulus and tensile strength is observed, accompanied by a decrease of deformability resulting in lower elongation at break and diminished toughness of the material [6]. At higher ller content, processing of the material is more difcult, related to a substantial increase in viscosity of the melt caused by a presence of the ller. While the increase of Youngs modulus and tensile strength with the increase of the ller content usually does not exceed one order of magnitude, the changes in deformation at break are quite dramatic in many cases, especially if a reinforcing ller, such as silica or carbon black, is used [7]. Nielsen [8] proposed rather simple equation for a description of the change

of the values of elongation at break b,c with increasing ller content b,c = 1 1/3 b,m (1)

assuming a random distribution of perfectly spherical ller. Nevertheless, the equation does not t for most real systems and other equations have been derived later [9]. Although the mechanisms of electrical conductivity and deformation behavior leading to mechanical fracture are completely different, certain phenomenological similarity exists when comparing the shape of the dependencies of the values on the concentration of the ller. Bearing this in mind, the dependencies of either electrical conductivity or elongation at break on the ller content have been compared and an attempt to explain the similarities was made. In this work, two grades of polyethylene were used as the matrix, namely high density polyethylene (HDPE, British Petroleum, UK) and low density polyethylene (LDPE, Bralen RA 2-19, Slovnaft, SK, MFI = 2.0 g/10 min) while carbon black Vulcan XC 72 (Cabot, UK) was used as the ller. The blends were prepared by mixing both components in a 50 ml mixing chamber of Brabender Plasticorder PLE 331 at 180 C for 10 min at the mixing speed 35 rpm. 1 mm thick slabs were prepared by compression molding of the mixed composite using a laboratory press Fontijne 200 (Netherlands) at 180 C for 3 min. The dog-bone specimens with a working area 35 3.6 1 mm were cut from the slabs. The mechanical properties were measured at RT using an Instron 4301 universal testing machine at deformation rate 10 mm min1 . For the electrical conductivity measurements the prepared composites were compression molded at 200 C for 2 min under 225 MPa. The thickness of the compression molded samples was about 0.2 mm. The volume electrical conductivity in polymer composites was measured according to ASTM D 257. Three electrode electrometer arrangement was used for the DCmeasurement of the resistance. The voltage level used varied in the range 0.1500 V. Silver paste was used to achieve good electrical contacts between the sample surface and the electrode of the conduction tester. The crystallinity of the samples was measured using a Perkin Elmer DSC 2 at heating rate 10 C min1 as a second melting run after normalized crystallization at 10 C min1 .

1999 Kluwer Academic Publishers

Figure 1 Relative electrical conductivity (c /m ) of the carbon black lled LDPE (circles) or HDPE (squares) as a function of the ller content ( ).

Figure 2 Relative values of elongation at break (b,c /b,m ) for the carbon black lled LDPE (circles) or HDPE (squares) as a function of the ller content ( ). Dotted lines = curve tting, dashed line = Nielsens model.

Electrical conductivities as a function of the ller content for two composites are shown in Fig. 1. Either low or high density polyethylene was used as the matrix and carbon black was added as ller. A signicant increase of conductivity is observed in a rather narrow concentration range of the ller. It is seen that the percolation threshold, i.e. the ller concentration at which the increase in conductivity occurs, differs for the two composites. In this case the percolation threshold c was determined as the inexion point on the dependence of electrical conductivity vs. ller concentration using the general equation log(c /m ) = A(1 ea )n (2)

the carbon black presence on the crystallinity was also found for HDPE composites. The dependencies of the values of elongation at break on the ller content are shown in Fig. 2. The elongation data are expressed as a ratio of elongation at break of the composite and the matrix b,c /b,m . The dependencies clearly demonstrate a dramatic drop in deformation after addition of a relatively small amount of the ller, which is higher than one order of magnitude, although the curves do not have a typical S-shape with the inexion point as in the case of the electrical conductivity dependencies. The experimental data were tted according to the equation b,c /b,m = exp(b ) (4)

where A, a and n are adjustable parameters, c and m are electrical conductivities of the composite and the matrix, and is the volume portion of the ller. The inexion point is determined via curve tting procedure according to i c = ln(n )/a (3)

The value was found to be 0.02 and 0.06 for the composite with HDPE and LDPE matrix, respectively. It is worth noting that the conductivities of HDPE and LDPE are very similar (around 1014 S m1 ) and the effect of matrix was marginal if high conductivities around 0.1 S m1 were reached for highly lled composites with either HDPE or LDPE matrix. Therefore the difference in percolation threshold concentration was ascribed to different crystallinity of the matrix (about 55 and 80% for LDPE and HDPE, respectively). In highly crystalline HDPE matrix a formation of more or less continuous conductive path is easier compared to composites with LDPE matrix where the higher amorphous portion may result in more homogeneous ller particles distribution. The crystallinity of the matrix is almost uninuenced by the presence of carbon black as demonstrated by DSC data. The values of heat of fusion were found to be 109.8 J g1 for LDPE and 107.3 J g1 (calculated on the LDPE content) for LDPE lled with 40 wt % of the carbon black. Negligible inuence of

where b is an adjustable parameter and b,c , b,m are relative elongations at break of the composites and matrix. The pseudopercolation threshold was determined as the intersection x of the tangents of the dependence in the beginning and in the end of the curve. In this case the relation between parameter b and x is reciprocal, i.e. b = 1/x . Equation 4 is a quite suitable empirical function to describe the relative change of deformation of the composite with increasing ller content. Curve tting using Equation 4 results in values of x of 0.01 and 0.05 for the composites with HDPE and LDPE matrices, respectively. Obviously, these values are very close to those calculated for the dependencies of electrical conductivities for the two matrices lled with carbon black. This result can be explained assuming that the electroconductive path is formed by the carbon black clusters in a close vicinity or even touching each other. It is reasonable to suggest that the clusters formed by the carbon black particles form a path not only for the fast electron transfer but also for microcracks which can grow easily into a crack of catastrophic size. The failure of particle-lled composites with thermoplastic ductile matrix can be initiated via a stress concentration on the ller particles. Thus small voids and cracks are formed which grow until reaching a critical crack size.

T A B L E I Elongation at break ( ) and standard deviation data ( S ) for different carbon black contents (CB) in high or low density polyethylene matrix (HDPE and LDPE, respectively) CB (wt %) 0 3 6 9 12 15 17 25 33 40 HDPE (%) 1429 213 245 157 50 63 43 4 S 46 59 152 40 17 41 29 1.5 LDPE (%) 554 341 207 S 57 95 148

110 22 10 4

28 11 3 2.5

The crack of critical length propagates almost instantaneously through the specimen. In the homogeneous material without the ller the formation and growth of cracks is random and the failure occurs at relatively high deformation. The presence of a ller results in both an easier initiation of crack formation via stress concentration on the ller surface on the one hand and in a decrease of chain mobility due to polymer-ller interactions resulting in lower deformability of the material on the other hand. Both effects contribute to a decrease of the elongation at break values. If the ller concentration is above a certain level the number of cracks created in the early stage of deformation is so high that a crack of a critical length can be formed by joining the numerous small voids and cracks present. It is proposed that if an electroconductive path is formed at a ller content corresponding to the percolation threshold, the crack of critical length is easily formed at an early stage of deformation through the microvoids and cracks present in the electroconductive path. The experimental data of elongation at break given as an average value of seven specimens are shown in Table I together with standard deviations. It is seen that while the standard deviations for matrix polymers are

in the range of a few percent from the original value, the experimental scatter for all the composites is much higher. It has to be admitted that the reason for this may be related to the specimen preparation since no additional treatment of the specimen surface (e.g. polishing the surfaces to remove aws) was made after the cutting procedure. Nevertheless, we believe that the scatter is caused mainly by the inherent inhomogeneities inside the material due to the presence of the ller aggregates and agglomerates. The observed empirical similarity between electrical and mechanical properties can be considered to be useful for a description of the dependencies of elongation at break on the ller content if the value of the percolation threshold is known. In this case the parameter x in Equation 4 should be substituted by the percolation ller concentration c which can be determined for electroconductive composites by independent measurement. Acknowledgment The authors appreciate the nancial support of Slovak grant agency VEGA (grant no. 2/5032/98). References
1. V . E . G U L , Structure and properties of conducting polymer composites (VSP BV, Utrecht, Tokyo, 1996). 2. J . G U R L A N D , J. Trans. Met. Soc. AIME 236 (1966) 642. T , Macromol. 3. C . K L A S O N , D . H . M c Q U E E N and J . K U B A Symp. 108 (1996) 247. 4. C . R A U W E N D A A L , J. Rheology 26 (1982) 572. 5. F . L U X , J. Mater. Sci. 28 (1993) 285. 6. J . A . M A N S O N and L . H . S P E R L I N G , Polymer blends and composites (Plenum Press, NY, 1976). K and I . C H O R V A T H , Macromol. Chem., Macromol. 7. I . C H O D A Symp. 75 (1993) 167. 8. L . E . N I E L S E N , J. Appl. Polym. Sci. 10 (1966) 97. 9. K . D . Z I E G E L , H . K . F R E N S D O R F F and A . V . F O G I E L , ibid. 13 (1969) 867.

Received 5 November 1998 and accepted 20 April 1999