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A vacuum circuit breaker has the circuit interrupting contacts inside a vacuum bottle. Without air the arc created by interrupting the circuit contains only material from the contacts. As a result the arc cannot sustain itself as well as it would if in air and the contacts will be able to handle higher currents.
In an SF6 breaker the arc occurs in SF6 gas. SF6 captures free electrons from the arc quickly quenching it. In the process SF6 is broken apart but will recombine back into SF6.
Some "SF6" breakers use vacuum bottles. This results in the small size of SF6 Switchgear with the advantages of vacuum breakers.
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