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@DiadDealer: That is because of windows DLL caching. On reboot the first time you start a program all its DLLs have to be loaded from disk. On subsequent restarts they are cached and already in RAM (assuming you have enough free RAM). Programs that do not use windows native frameworks have a particularly large number of DLLs to load. So the difference between cold and hot starts is much more noticeable.
@BetterRed: That is because a restart waits for calibre to shutdown cleanly first, which takes a few seconds.
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