A group of polyethylene|carbon black (PE|CB) composites was prepared with different CB volume fraction and the dependence of conductivity on the CB volume fraction was measured. The conductive percolation phenomenon of those composites was studied by Monte Carlo method. It was supposed that the conduction of those composites was not only dependent on the contact pathway formation but also on the quantum mechanical tunnel formation. The put in particle number dependence of “the conductive conjunction” number and “the partial conducting pathway” number and “the average particle number” in the partial conducting pathway was showed in three figures, respectively. The typical CB particle conjunct states obtained by Monte Carlo method were illustrated with “the conductive conjunction”, “the partial conducting pathway”, and “the conducting pathway” in different marks. Thus it vividly demonstrates the internal reason for the conductive percolation of the PE|CB composites. It is worth notice that only more than 50% CB particles are connected together to form the conducting pathway when the conductive percolation takes place, and that in the system there still exist some partial conducting pathways. The later does not make contribution for the conductivity of the PE|CB composites.
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