[Abridged] Inverse Compton scattering of CMB fluctuations off cosmic electron plasma generates a polarization of the associated Sunyaev-Zeldovich (SZ) effect. This signal has been studied so far mostly in the non-relativistic regime and for a thermal electron population and, as such, has limited astrophysical applications. Partial attempts to extend this calculation for a thermal electron plasma in the relativistic regime have been done but cannot be applied to a general relativistic electron distribution. Here we derive a general form of the SZ effect polarization valid in the full relativistic approach for both thermal and non-thermal electron plasmas, as well as for a generic combination of various electron population co-spatially distributed in the environments of galaxy clusters or radiogalaxy lobes. We derive the spectral shape of the Stokes parameters induced by the IC scattering of every CMB multipole, focusing on the CMB quadrupole and octupole that provide the largest detectable signals in galaxy clusters. We found that the CMB quadrupole induced Stoke parameter Q is always positive with a maximum amplitude at 216 GHz which increases slightly with increasing cluster temperature. The CMB octupole induced Q spectrum shows, instead, a cross-over frequency which depends on the cluster electron temperature, or on the minimum momentum p_1 as well as on the power-law spectral index of a non-thermal electron population. We discuss some possibilities to disentangle the quadrupole-induced Q spectrum from the octupole-induced one which allow to measure these quantities through the SZ effect polarization. We finally apply our model to the realistic case of the Bullet cluster and derive the visibility windows of the total, quandrupole-induced and octupole-induced Stoke parameter Q in the frequency ranges accessible to SKA, ALMA, MILLIMETRON and CORE++ experiments.
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