Spray frozen, freeze dried nitrate powder with composition Bi:Pb:Sr:Ca:Cu 1.7:0.3:2.0:2.5:3.5 has been thermally decomposed (up to 870 degreesC). In situ neutron diffraction investigations during heating and cooling of the powder have been performed at DN2 instrument from the IBR2 reactor at JINR, Dubna, Russia. Phase formation and reformation and domains of stability for different phases were observed and discussed.