N.C. Collier

Development of magnesium phosphate cements for encapsulation of radioactive waste

Abstract Abstract Radioactive waste streams that include metallic uranium are incompatible with conventional ordinary Portland cement (OPC)-based encapsulation matrices. These encapsulation systems are essentially composite materials that incorporate high replacement levels of pulverised fly ash (PFA) or blast furnace slag (BFS). A potential alternative encapsulant for the treatment of problematic waste streams is magnesium phosphate cement. This paper discusses the fundamental characterisation results obtained from two magnesium phosphate cement formulations being developed in the UK for the encapsulation of metallic intermediate level waste (ILW). When compared to conventional OPC based systems, the two magnesium phosphate cement formulations investigated have lower pH, are able to chemically combine more mix water into the system and provide sufficient workability at water/solid ratios close to the theoretical confines needed for paste saturation. The results presented have confirmed compliance of this material against NDA RWMD guidelines for strength and expansion. The X-ray diffraction (XRD) and differential scanning calorimetry (DSC) results obtained for both formulations up to 360 days cure time have indicated that the cement system shows evidence of chemical stability.

Theoretical development and validation of a Sharp Front model of the dewatering of a slurry by an absorbent substrate

The absorption of water from a slurry into an absorbent substrate is analysed using Sharp Front theory. The analysis describes the relationship between the sorptivity S of the substrate, the desorptivity R of the slurry and the transfer sorptivity A between slurry and substrate, and leads to the relationship 1/A2 = 1/R2 + 1/S2. Experimental data are presented which validate this equation for the practically important case of the absorption of water from soft mortar mixes by fired clay bricks. A unique feature of the experimental work is the measurement of the desorptivity of the mortars at a pressure equal to the wetting front capillary pressure of the clay brick substrate. Analysis of the experimental data also enables, for the first time, the calculation of the capillary potential at the slurry/substrate interface. The analysis has relevance to many aspects of ceramic and mineral processing, industrial filtration and construction engineering.

Phosphate modified calcium aluminate cement for radioactive waste encapsulation

Abstract Abrstract The present study is part of a wider investigation to develop an alternative cementing system for the encapsulation of problematic low and intermediate level radioactive waste. It has been suggested that alternative cementing systems, with lower internal pH than conventional Portland cement based composite cements, may reduce the corrosion of some reactive metals and may be beneficial for the long term durability of wasteforms. A potential alternative is an acid–base cementing system, based on mixing calcium aluminate cement (CAC) with acidic phosphate solutions. Although these systems have been studied previously, there has been no systematic investigation to identify phosphates for producing suitable matrixes for application in radioactive waste encapsulation. In the current study, monophosphate modified CAC formulations did not set or develop significant strength, whereas polyphosphate modified CAC formulations exhibited rapid setting and strength development. It is proposed that polyphosphate modified systems form amorphous reaction products, which act as binders between the partially and unreacted CAC particles, and were responsible for high strength development. Thermogravimetric analysis and scanning electron microscopy results suggest that this binding matrix consists of amorphous calcium phosphate and alumina gel. The results presented in this investigation suggest that polyphosphate modified CAC has potential as an alternative cementing system for radioactive waste encapsulation.

Long term leachate evolution during flow-through leaching of a vault backfill (NRVB)

Abstract Some of the illustrative concepts for the disposal of intermediate-level waste in a geological disposal facility in the UK employ a cementitious backfill around the waste packages. The concept for higher strength rocks would use a highly alkaline backfill composed of Portland cement (now known as CEM I), hydrated lime and limestone flour, referred to as Nirex reference vault backfill (NRVB). This paper reports a study of the extensive leaching of cured NRVB in a range of generic leachant compositions (deionized water, 0.1 м and 1 м NaCl solutions) under flow-through conditions using a flexible wall permeameter. The experiments were designed to run for up to two years and to pass at least 1000 volumes of leachant (defined as the cumulative leachate volume produced/NRVB solid specimen volume) through the NRVB samples. Results for the pH evolution profiles of the leachates and the microstructural analysis of the unleached and leached samples are presented.

Corrosion and expansion of grouted Magnox

Abstract With potential storage of several hundred years underground in a geological disposal facility (GDF) before closure, there is a requirement for radioactive waste packages to perform adequately. Over the past 25 years, cementitous grouts based on blast furnace slag (BFS) and ordinary Portland cement (OPC), have been used in the UK to immobilize intermediate-level waste (ILW), Magnox swarf, and currently such wasteforms are in surface storage awaiting geological disposal. Magnox fuel cladding will slowly corrode when encapsulated in alkaline cementitious grouts to produce hydrogen gas and an expansive corrosion product. Expansive corrosion products may lead to degradation of the wasteform and, if extensive, could affect the container. This study investigated the acute and chronic rates of corrosion of unirradiated Magnox swarf encapsulated in a BFS/OPC grout over a range of temperatures (25, 40, 60, 75 and 90ºC) for curing times of up to 2½ years. Structural product degradation starts to develop as the tensile strength of the grout is approached by the expansive forces generated. Deformation of some experimental containers was also noted. An estimate of the time taken for a grouted product to fracture from this study due to the corrosion solely of Magnox is 350 years for storage at 25ºC. Although not fully described in this paper, the main cement phases were calcium silicate hydrate, portlandite and gehlenite; the main product of Magnox corrosion was brucite. The curing temperature did not affect the compositions of the Magnox metal, corrosion product or grout.

The Effect of Supplementary Pulverised Fuel Ash on Calcium Aluminate Phosphate Cement for Intermediate-Level Waste Encapsulation

The objective of the current study was to evaluate the effects of supplementary pulverised fuel ash on phosphate-modified calcium aluminate cement. These systems are being established as part of a wider project to develop alternative cementing systems for the encapsulation of problematic low- and intermediate-level radioactive waste in the UK.

Release of uranium from candidate wasteforms

Abstract Large volumes of depleted natural and low-enriched uranium exist in the UK waste inventory. This work reports on initial investigations of the leaching performance of candidate glass and cement encapsulation matrices containing UO3 powder as well as that of uranium oxide powders. The surface areas of UO3 powder and the monolith samples of UO3 conditioned in the glass and cement matrices were very different making leaching comparisons difficult. The results showed that for both types of monolith conditioned samples a steady increase of uranium concentration in solution with time was generally not observed. The wt.% of uranium leached from UO3 conditioned in the lead borosilicate glass wasteform was approximately five orders of magnitude less than that leached from UO3 powder. Similarly, the quantities of uranium leached from UO3 conditioned in composite cement made with ordinary Portland cement, and from magnesium phosphate cement, were approximately four and three orders of magnitude, respectively, less than that leached from UO3 powder. The performance of a mixed oxide borosilicate glass wasteform was only slightly better than that of UO3 powder. This work shows that wasteforms based on encapsulation in lead borosilicate glass and cement matrices have the greatest potential for further development.