My previous post is C#. Translation to vb.net follows:
Private Sub ThisApplication_ItemSend(ByVal item As System.Object, _
ByRef cancel As Boolean) _
Handles Application.ItemSend
cancel = False
Dim mailItem As Outlook._MailItem = TryCast(item, Outlook._MailItem)
If mailItem IsNot Nothing Then
'Call you winform here
End If
End Sub
Note: I do not have vb.net installed at home. The vb.net may contain compile errors.