Polytetrafluoroethylene (PTFE) is a semi-crystalline polymer, which has been employed in a range of engineering applications due to its extremely low coefficient of friction, resistance to corrosion, and excellent electrical insulation properties. Despite failure-sensitive applications such as surgical implants, aerospace components, motor seals, and barriers for hazardous chemicals, the mechanisms of crack propagation in PTFE have received limited coverage in the literature. Moreover, PTFE exhibits complex crystalline phase behavior that includes four well-characterized phases with both local and long range order. Three crystalline structures (phases II, IV, and I) are observed at atmospheric pressure with transitions between them occurring at 19 and 30 degrees C. This observation provides a unique opportunity for investigation of the effects of a polymers crystalline phase on fracture and microstructure evolution. Moreover, due to the presence of three unique ambient pressure phases near room temperature, it is essential to develop an understanding of the effects of temperature-induced phase transitions on fracture mechanisms of PTFE to prevent failure over the normal range of operating temperatures. In this work, we present values for the J-integral fracture toughness of PTFE for a range of temperatures and loading rates employing the single specimen normalization technique. Crack propagation in PTFE is found to be strongly phase dependent with a brittle-to-ductile transition in the crack propagation behavior associated with the two room temperature phase transitions. Increases in fracture toughness are shown to result from the onset of stable fibril formation bridging the crack plane and increased plastic deformation. The stability of drawing fibrils is primarily determined by temperature and crystalline phase with additional dependence on loading rate and microstructure anisotropy. [LAUR-05-0004] (c) 2005 Elsevier Ltd. All rights reserved.