We report an explosive boiling in a Zr-based (Vitreloy 1) bulk metallic glass irradiated by a nanosecond pulse laser with a single shot. This critical phenomenon is accompanied by the ejection of high-temperature matter from the target and the formation of a liquid-gas spinodal pattern on the irradiated area. An analytical model reveals that the glassy target experiences the normal heating (melting) and significant superheating, eventually culminating in explosive boiling near the spinodal limit. Furthermore, the time lag of nucleation and the critical radius of vapor bubbles are theoretically predicted, which are in agreement with the experimental observations. This study provides the investigation on the instability of a metallic glass liquid near the thermodynamic critical temperature.

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