I agree, all my overflows are glass/glass... this allows me to get the previously mentioned BLACK glass. I really like the look, the only problem with glass though is that you cannot cut the notches in the top, as you can with acrylic. I also have tried silicone acrylic to glass.. no truely promising results... an occasional success, but random. Anyone doing so, should get themselves insured, as sooner or later they will flood themselves, or some other poor soul. I think about an overflow on my system breaking off the ourside... this would drain the tank down 4-5" plus everything in the sump that is being returned. 65 gallons... maybe more... NO THANK YOU.
I see the point you are making about siliconing the overflows INTO a system like those from ALL-GLASS and OCEAINIC and others...
Picture this... make a 10 gallon tang with acrylic and held together with silicone. float it like a boat. The water pressure will keep it together.
Now.. fill the same tank with water... and wait... it will eventually fall apart or leak.
BTW, I like to scrape the algae or coraline off my overflow from time to time, try that with acrylic without scratching or breaking it.
J