Right click on the icon > open with > choose program (right at the bottom ignore suggested list) you will then get a list of programs with a tick box at the bottom always use this program for this file type, tick box first then choose word
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Synology invite you to their launch event on 16th September 2015. See the unveiling of the new DSM and products live, plus a chance to win a populated NAS! Tickets are free and available now. Click HERE for more details