If you cannot create a Volumill toolpath the first thing to check is your license manager. Be sure that your license is active.
If the license is active and you still cannot create a Volumill toolpath you may have had issues in installation.
Navigate to C:\ProgramFiles\CAMWorks2014x64\CAMWorks_VC10\volumill on your system.
Open the file CWVoluMillAppu.exe
If you receive an error opening this file, you will need to choose the following fix for either 32 or 64 bit systems:
Open CAMWorks and your Volumill toolpath should now function.