This article reviews structural phase transitions of Zintl-phase silicide BaSi
2 at high pressures and high temperatures and a formation of Si clathrate Ba
8Si
46 from an 8:30 molar mixture of BaSi
2 and Si at high pressures and high temperatures. At pressures ranging from 0 to 10 GPa and temperatures ranging from 300 to 1300 K, BaSi
2 has four phases: BaSi
2 phase, EuGe
2 phase, SrSi
2 phase, and BaSi
2-IV phase. When heated at approximately 5 GPa, BaSi
2 undergoes the three structural phase transitions: the BaSi
2-to-EuGe
2, the EuGe
2-to-SrSi
2, and the SrSi
2-to-BaSi
2-IV transitions. At 4.3 GPa, Ba
8Si
46 is formed by a solid state reaction of an 8:30 molar mixture of SrSi
2-phase BaSi
2 and Si after BaSi
2 undergoes the BaSi
2-to-EuGe
2 and the EuGe
2-to-SrSi
2 transitions. The structural phase transitions of BaSi
2 and formation process of Ba
8Si
46 are discussed comparing it with structural phase transitions of SrSi
2 and of an 8:30 mixture of SrSi
2-pahse SrSi
2 and Si.
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