In the current study, polylactic acid/high density polyethylene/carbon black (PLA/HDPE/CB) composites are prepared via a two‐step method. A double percolation network with co‐continuous structure and filler distribution at the interface is constructed to design conductive polymer composites with low percolation threshold. The controllable distribution of CB at the interface is achieved by appropriate processing procedures involved mixing sequence and mixing time by taking advantage of the migration of CB from the unfavorable PLA phase to the favorable HDPE phase. Morphology characterization reveals that when the mixing time of the added HDPE is 3 min, the formation of co‐continuous structure of PLA/HDPE (60/40, w/w) is observed, and CB particles migrate to the co‐continuous interface. The electrical conductivity measurement shows that such double percolation conductive network reduces the percolation threshold of PLA/HDPE/CB to 2.42 wt%. The rheological property proves the establishment of particle percolation network, and the rheological percolation threshold is determined as 1.20 wt%. The prepared PLA/HDPE/CB composite by the two‐step method displays a notably low percolation threshold than that prepared by one‐step simultaneous mixing. Moreover, this strategy presents a high potential application in the fabrication of conductive polymer composites involving other miscible multiphase systems.
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