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Neutron stars are composed (mostly) of neutrons because during the star's life, the fusion processes strip apart atoms, leaving the electrons behind inside the star's core. When the star runs out of fuel and fuses up the atomic chain and hits nickel, it collapses. The pressure from the collapse is enough to force all those electrons together and as you compress them more and more, the free protons from the fusion processes bond with the electrons, forming neutrons.

Put simply, it's mostly neutrons because it's just doesn't have enough mass to be made of mostly quarks or become a singularity.

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