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I had a frame that looked like the third one brought into me last year for re-framing. Poly moulding hanging above the fireplace, the customer had lit a candle on the mantelpiece underneath it....
I did once try to make an arch-top frame for a mirror using poly moulding. Heated the top rail and bent it on a former.
Worked up to a point. You really need a oven.
Years ago, long before poly moulding, I too tried to make an arch-top frame. I spent hours making fine saw cuts in the moulding starting from the rebate and stopping halfway through the stick, the cuts spaced evenly along a 2' length. To make the wood more pliable I held the length over a boiling kettle hoping the steam would soften the wood, allowing the length to bend by closing the saw cuts.
The theory was sound enough but the whole exercise was a complete failure and a total waste of time