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The phase behaviour and phase transition of the tetradecyldimethylaminoxide micellar system TDMAO/ D2O have been investigated by small-angle neutron scattering (SANS) at temperatures T between 287 and 325 K, pressures up to P = 842 MPa and at TDMAO concentrations of 55 and 102 mmol l−1. A pressure-induced structural (shape) phase transition was observed for the whole pressure versus temperature range, with a slope of the transition line of dTm/dP ≃ 0.31° MPa−1. The reversibility and reproducibility of this phase change were tested. The SANS experiments showed a pressure-induced structural phase transition from a low-pressure phase (i), where rod-like micelles with a radius of R = 1.94 ± 0.03 nm were present, to a high-pressure phase (ii). An accurate determination of the structure of phase (ii) has not been possible up to now. In phase (ii), a discrete correlation peak in the Q range 1.8–2.2 nm−1 was found.

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