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Under very hot temperatures — greater than 100,000,000 Kelvin (179,999,540.6 F) — the helium nuclei begin to fuse, first as pairs into unstable 4-proton beryllium nuclei, and eventually, as enough beryllium nuclei blink into existence, into a beryllium plus a helium.
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In older stars that have burned most of their hydrogen, leftover helium accumulates.