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This is all down to how good a material can conduct heat. Metals conduct heat much more readily than wood. This means that if you were to heat the ends of 2 identically sized rods, 1 of steel and 1 of wood, (think of 12" steel and wooden rulers) the heat would travel down the steel ruler faster than the wooden one. So back to the bench - there are 2 things happening to make the metal bench feel hotter. 1) The heat from the sun would heat the metal faster than the wood because of the good conductivity of the metal, so the metal could actually be hotter. 2) If the metal and wooden benches had been in the sun long enough for them to have reached the same temperature, then because the metal conducts heat better than the wood, when you touch the metal bench it "feels" hotter because the metal is far better at transferring the heat away from itself and into your hand than the wooden bench is. This also works for cold items. A card/paper carton of juice taken from the fridge does not feel as cold as a metal can of drink standing next to it, again this is because the metal conducts heat better than the card/paper.

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