ABSTRACT
Portland cement is extensively used for the conditioning of radioactive waste. However, its high alkalinity is a serious obstacle to the stabilization of waste containing aluminum metal since aluminum is oxidized by the pore solution with the production of dihydrogen. This work investigates the potential of an alternative binder, magnesium potassium phosphate (MKP) cement, for the stabilization of Al-Mg alloys comprising 2 to 4.5 wt% of Mg and other metallic impurities. The objective is to assess the influence of the alloy composition on its reactivity in the cementitious matrix at earlier ages, as well as at later ages, when the cement has reached a significant reaction degree. Two complementary techniques are used. Gas chromatography shows that the dihydrogen release, resulting from the corrosion process, is not influenced by the magnesium content in the alloy. Electrochemical impedance spectroscopy provides qualitative information about the corrosion but also makes it possible to assess the corrosion current using an equivalent electrical circuit linked to the kinetic parameters of the postulated corrosion mechanism. Over a one-year period, the corrosion current of the alloys, regardless of their Mg content, is reduced by almost three orders of magnitude in MKP mortar as compared to Portland-cement-based mortar.
ABSTRACT
To assess the potential of calcium sulfoaluminate cement to solidify and stabilize wastes containing high amounts of soluble zinc chloride (a strong inhibitor of Portland cement hydration), a simulated cemented waste form was submitted to leaching by pure water at a fixed pH of 7 for three months, according to a test designed to understand the degradation processes of cement pastes. Leaching was controlled by diffusion. The zinc concentration in the leachates always remained below the detection limit (2 µmol/L), showing the excellent confining properties of the cement matrix. At the end of the experiment, the solid sample exhibited three zones which were accurately characterized: (i) a highly porous and friable surface layer, (ii) a less porous intermediate zone in which several precipitation and dissolution fronts occurred, and (iii) the sound core. Ettringite was a good tracer for degradation. The good retention of zinc by the cement matrix was mainly attributed to the precipitation of a hydrated and well crystallized phase with platelet morphology (which may belong to the layered double hydroxide family) at early age (≤ 1 day), and to chemisorption onto aluminum hydroxide at later age.
Subject(s)
Aluminum Compounds/chemistry , Calcium Compounds/chemistry , Chlorides/chemistry , Construction Materials , Sulfur Compounds/chemistry , Zinc Compounds/chemistry , Zinc/chemistry , Hydrogen-Ion ConcentrationABSTRACT
The potential of calcium sulfoaluminate (CSA) cement was investigated to solidify and stabilize wastes containing large amounts of soluble zinc chloride (a strong inhibitor of Portland cement hydration). Hydration of pastes and mortars prepared with a 0.5 mol/L ZnCl(2) mixing solution was characterized over one year as a function of the gypsum content of the binder and the thermal history of the material. Blending the CSA clinker with 20% gypsum enabled its rapid hydration, with only very small delay compared with a reference prepared with pure water. It also improved the compressive strength of the hardened material and significantly reduced its expansion under wet curing. Moreover, the hydrates assemblage was less affected by a thermal treatment at early age simulating the temperature rise and fall occurring in a large-volume drum of cemented waste. Fully hydrated materials contained ettringite, amorphous aluminum hydroxide, strätlingite, together with AFm phases (Kuzel's salt associated with monosulfoaluminate or Friedel's salt depending on the gypsum content of the binder), and possibly C-(A)-S-H. Zinc was readily insolubilized and could not be detected in the pore solution extracted from cement pastes.
