Waste processing at the Savannah River Plant will involve reconstitution of the salts (NaNO3, NaNO2, Na2 SO4 and NaOH) into a concentrated solution followed by solidification in a cement-based waste form. Phase stability and mechanical durability of this material will depend to a considerable extent on the thermal properties of the waste form. Fly ash has been used to moderate the hydration and setting processes so as to avoid high temperatures which could cause thermal stresses. Both high-calcium (Class C) and low-calcium (Class F) fly ashes were studied. Other constituents of the mixes include granulated blast furnace slag and finely crushed lime-stone. The adiabatic temperature increases and thermal conductivities were measured and related to matrix mineralogy and microstructure as determined by x-ray diffraction and scanning electron microscopy, respectively.