Cements in Radioactive Waste Disposal

The use of cement and concrete to immobilise radioactive waste is complicated by the wideranging nature of inorganic cementing agents available as well as the range of service environments in which cement is used and the different functions expected of cement. For example, Portland cement based concretes are widely used as structural materials for construction of vaults and tunnels. These constructions may experience a long pre-closure performance lifetime during which they are required to protect against collapse and ingress of water: strength and impermeability are key desirable characteristics. On the other hand, cement and concrete may be used to form backfills, ranging in permeability. Permeable formulations allow gas readily to escape, while impermeable barriers retard radionuclide transport and reduce access of ground water to the waste. A key feature of cements is that, while fresh, they pass through a fluid phase and can be formed into any shape desired or used to infiltrate other materials thereby enclosing them into a sealed matrix. Thereafter, setting and hardening is automatic and irreversible. Where concrete is used to form structural elements, it is also natural to use cement in other applications as it minimises potential for materials incompatibility. Thus cementmainly Portland cementhas been widely used as an encapsulant for storage, transport and as a radiation shield for active wastes. Also, to form and stabilise structures such as vaults and silos. Relative to other potential matrices, cement also has a chemical immobilisation potential, reacting with and binding with many radionuclides. The chemical potential of cements is essentially sacrificial, thus limiting their performance lifetime. However performance may also be required in the civil engineering sense, where strength is important, so many factors, including a geochemical description of service conditions, may require to be assessed in order to predict performance lifetime. The nature of Portland cement is explained. Portland cement is the most widely used cement type and benefits from technology transfer from civil engineering research; also of the more than 150 years of experience of its durability and performance in a range of service environments. The origin of the chemical binding potential of cement arises from a combination of mechanisms: chemisorption on cement solids, incorporation by solid solution in cement solids and, at higher concentrations, precipitation of a solubility-limiting phase or phases in a calcium rich, high pH environment. These favourable potentials, especially pH conditioning, are, as noted, essentially sacrificial: cement must dissolve or react to maintain these conditions in the course of its service life. However the immobilisation potential will also change with time, even in isolation, because cement minerals undergo internal aging and slow reaction with other materials in the near field. Much research has been conducted, often on an empirical basis, leading to the characterisation of these potentials and of their time dependence. Yet the picture which emerges is incomplete and of variable quality. New research is described which, it is expected, will lead to a more scientific basis for the extrapolation of presentday cement performance into the future. The high pH of Portland cement matrices has advantages but also, disadvantages. For example, Portland cement gives excellent protection against corrosion to embedded steel but, on the other hand, it corrodes electropositive metals with evolution of hydrogen. Formation of a high pH “plume” may also spread from the concrete to the near field, degrading other barriers such as bentonite and affecting the sorptive potential of the near field for radionuclides. These considerations have led to the search for alternative lower pH cements which are less alkaline than Portland cement. A description of some common types is given. However alternative choices present a burden of proof because with few exceptions, much less is known about their ability chemically to immobilise waste species and their longterm durability relative to Portland cement in a range of natural environments. It is concluded that the most robust of these alternative formulations are based on calcium aluminate and sulfoaluminate cements, on magnesium phosphate and on geopolymers.