This paper investigates the security at the physical layer of cooperative relay communications. Inspired by the principle of physical-layer network coding (PNC), we propose a new secure relaying scheme, namely secure PNC-based modify-and-forward (SPMF). In the proposed scheme, the relay node linearly combines the decoded data from the source node with an encrypted key before conveying the mixed data to the destination node. As both the linear PNC operation and encrypted key at the relay are unknown to the eavesdropper, the SPMF scheme provides a double security level in the system. Particularly, taking into account the practical scenario of the imperfect knowledge shared between the relay and destination, the secrecy outage probability (SOP) of the proposed SPMF scheme is analysed and evaluated in comparison with modify-and-forward, cooperative jamming, decode-and- forward and direct transmission schemes. The proposed scheme is shown to achieve a performance improvement of up to 3 dB when compared to the conventional schemes under imperfect knowledge of shared information between the nodes.