Brilliant question! And the answer is pretty good, too.
Corn kernels consist of a hard moisture sealed hull and a dense interior consisting mostly of starch, but also some water, oils and proteins. As the kernels are heated, the water and oils expand within the hard hull and turn into steam (the temperature get up to 180 degrees C!) and create high pressure. Under these conditions the starch inside the kernel puffs up and softens. This expansion causes the pop. The starch and protein then set in the familiar popcorn shape as they cool.
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