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When you have Word as the e-mail editor you must have a default signature configured or you won't be able to select another signature while composing the mail. To select another signature right click on the left side of the signature and a list of available signatures will pop-up. If you don't want a default signature you can easily workaround this by configuring an empty signature (just containing spaces or Enters or a single dot) as the default signature. This will still enable the right click menu so you can choose a signature when you want to.
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Rich Text Format (RTF) A Microsoft format that supports text formatting, bullets, and alignment. You can also use signatures with Outlook Rich Text. (If you're using Microsoft Word as your e-mail editor, you must create the signature in Word.) Outlook Rich Text can be read only by Microsoft Exchange Client versions 4.0 and 5.0, Outlook 97, Outlook 98, and Outlook 2000. (Outlook Express cannot read RTF). In addition to messages, Outlook meeting requests and task requests are sent in RTF format, too.