A systematic study of single crystalline Tb₅Si_2.2Ge_1.8, including magnetic field induced crystallographic and magnetic phase transformations, magnetocaloric effect, ferromagnetic short-range correlations, electrical resistivity, magnetoresistance, and spontaneous generation of voltage (SGV) has been presented. A study of SGV in single crystalline Gd₅Si₂Ge₂ and Gd has also been included.

The metamagnetic-like transitions and giant magnetocaloric effect were observed with the magnetic field applied parallel to the a- and c-axes, but not the b-axis in a Tb₅Si_2.2Ge_1.8 single crystal. The in-situ x-ray powder diffraction study indicates that these metamagnetic-like transitions are coupled to a crystallographic phase transformation occurring via strong magnetoelastic interactions. The magnetocrystalline anisotropy plays an important role in this system. Magnetic fields less than 40 kOe can not drive either the magnetic or the crystallographic phase transition to completion for Tb₅Si_2.2Ge_1.8 powder due to the strong single ion anisotropy of Tb.

Magnetic field dependencies of the critical temperatures of magnetic phase transitions of Tb₅Si_2.2Ge_1.8 are highly anisotropic for both the main magnetic ordering process occurring around 120 K and a spin reorientation transition at ~70 K. Magnetic-field-induced phase transitions occur with the magnetic field applied isothermally along the a-and b-axes (but not along the c-axis) between 1.8 and 70 K in fields below 70 kOe. Strongly anisotropic thermal irreversibility is observed in the Griffiths phase regime between 120 and 200 K with applied fields ranging from 10 to 1000 Oe. Our data: (1) show that the magnetic and structural phase transitions around 120 K are narrowly decoupled; (2) uncover the anisotropy of ferromagnetic short-range order in the Griffiths phase; and (3) reveal some unusual magnetic domain effects in the long-range ordered state of the Tb₅Si_2.2Ge_1.8 compound. The temperature-magnetic field phase diagrams with field applied along the three major crystallographic directions have been constructed.

The positive colossal magnetoresistance (CMR) with a magnitude of ~150% was observed with the magnetic field applied parallel to the a-axis, but not the b- and c-axes in Tb₅Si_2.2Ge_1.8 single crystals. The electrical resistivity shows a low-temperature high-resistivity behavior (i.e. the resistivity at low temperature is higher after the transformation to the low temperature phase than the resistivity of the phase before the transition) along the a-axis, contrary to those along the b- and c-axes. The positive CMR effect originates from an intrinsic crystallographic phase coexistence state frozen below the Curie Temperature (T_C). The differences in the temperature dependencies of electrical resistivities and longitudinal magnetoresistance along the a-axis and those along the b- and c-axes can be explained by the geometry of the phase boundaries at low temperatures, and the inability of the external magnetic field to induce the crystallographic phase transformation along the b- and c-axes.

Temperature-induced SGVs were observed along all three principal crystallographic axes of Tb₅Si_2.2Ge_1.8, but not in Gd. Field-induced SGVs were observed with magnetic fields less than 40 kOe applied along the a-axis of Tb₅Si_2.2Ge_1.8, and the c-axis of Gd. The absence of the temperature induced SGV in Gd indicates the key role first-order phase transformations play in the appearance of the effect when temperature varies. The anisotropy of magnetic field induced SGV in Tb₅Si_2.2Ge_1.8 and the existence of field induced SGV in Gd, highlight the importance of the magnetocaloric effect in bringing about the SGV. In single crystal and polycrystalline Gd₅Si₂Ge₂ during the coupled magneto-structural transformations, reversible and repeatable SGV responses of the materials to the temperature and magnetic field have been observed. The parameters of the response and the magnitude of the signal are anisotropic and rate dependent. The magnitude of the SGV signal, and the critical temperatures and critical magnetic fields at which the SGV occurs vary with the rate of temperature and magnetic field changes.