Development of low-pH cements for immobilisation of intermediate level radioactive waste: Achievements and challenges

Although cementation is a widely recognized solidification/ stabilization process for immobilisation of Intermediate Level Radioactive Waste (ILRW), the low resistance to hyperalkaline pore waters compromises the effectiveness of the process when Portland Cement (PC) is employed. Moreover the manufacture of PC is responsible for significant CO2 emissions. In this context, low pH cements are environmentally more suitable and have emerged as a potential alternative for obtaining secure waste forms. This paper summarises the achievements on development of low-pH cements and the challenges of using these new materials for the ILRW immobilisation. The performance of waste forms is also discussed in terms of radionuclides release. Reactive magnesium oxide and magnesium phosphate cements are emphasised as they feature important advantages such as consumption of available constituents for controlling acid-base reactions, reduced permeability and higher density. Additionally, in order to identify new opportunities for study, the long-term modelling approach is also briefly discussed. Copyright © 2013 by ASME.

Oxidative dehydrogenation of ethane and propane over Mn-based catalysts

The catalytic performances of Mn-based catalysts have been investigated for the oxidative dehydrogenation of both ethane (ODE) and propane (ODP). The results show that a LiCl/MnOx/PC (Portland cement) catalyst has an excellent catalytic performance for oxidative dehydrogenation of both ethane and propane to ethylene and propylene, more than 60% alkanes conversion and more than 80% olefins selectivity could be achieved at 650 degrees C. In addition, the results indicate that Mn-based catalysts belong to p-type semiconductors, the electrical conductivity of which is the main factor in influencing the olefins selectivity. Lithium, chlorine and PC in the LiCl/MnOx/PC catalyst are all necessary components to keep the excellent catalytic performance at a low temperature.

Study of Mn-based catalysts for oxidative dehydrogenation of cyclohexane to cyclohexene

The gas-phase oxidative dehydrogenation (ODH) of cyclohexane to cyclohexene in the presence of molecular oxygen has been studied over various Mn-based catalysts. It is found that LiCl/MnOx/PC (Portland cement) catalyst exhibits the highest catalytic performance, and a 42.8% cyclohexane conversion, 58.8% cyclohexene selectivity and 25.2% cyclohexene yield can be achieved under 600 degrees C, 20,000 h(-1) and C6H12/O-2/N-2= 14/7/79. There are good correlations between the selectivities to cyclohexene and the electrical conductivities of Li doped Mn-based catalysts, from which it is deduced that the non-fully reduced oxygen species (O-2(-), O-2(2-), O-) involved in a new phase of LiMn2O4 might be responsible for the high selectivity toward cyclohexene, whereas the Mn2O3 crystal phase results in the COx formation. The selectivity to cyclohexene increases with increasing molar ratio of Li to Mn in LiCl/ MnOx/PC.

The Medway Valley: a Kent landscape transformed

In 1750 the lower Medway Valley, the area between the towns of Maidstone and Rochester, was firmly part of Kent's 'Garden of England'. A century later, this tranquil, agrarian landscape had been transformed into a hive of industry and commerce, through the emergence of papermaking, cement manufacture, brickmaking, brewing, ship and barge building, seed crushing and engineering. The lower Medway Valley became synonymous with the production of Portland cement, stock bricks and the steam engines of Aveling and Porter, yet, by the end of the Second World War, much of this industry was gone. "The Medway Valley: A Kent Landscape Transformed", the first Victoria County History publication in Kent for over 75 years, charts this cyclical story of landscape change. It explores how the quiet, rural landscape of a collection of eight riverside parishes around Rochester was dramatically transformed during industrialization, before returning to its formal rural state. This volume traces the impact of industrial development and decline on the valley and its people. It details changing patterns of work and society, the creation of new settlements and the pivotal role of the river in all aspects of village life reflecting two centuries of change and upheaval.

The use of mineral trioxide aggregate in endodontics - status report

Mineral trioxide aggregate (MTA) is a clinical product comprising a mixture of Portland cement and bismuth oxide which is currently used as a root−filling material in dentistry. It has good biological compatibility, is capable of promoting both osteogenesis and cementogensis, and is finding increasing use in endodontic therapy. It is dimensionally stable, and provides an acceptable and durable seal for endodontically treated teeth. This article reviews the chemistry and applications of MTA, and highlights the fact that very little is currently known about the hydration chemistry, phase evolution and stability of this cement in physiological environments. However, biological effects of MTA have been well documented and are considered in detail. The article concludes that this material is a useful addition to the range of materials available for clinical application in endodontics.

Comparison of properties of traditional and accelerated carbonated solidified/stabilized contaminated soils

The investigation of the long-term performance of solidified/stabilized (S/S) contaminated soils was carried out in a trial site in southeast UK. The soils were exposed to the maximum natural weathering for four years and sampled at various depths in a controlled manner. The chemical properties (e.g., degree of carbonation (DOC), pH, electrical conductivity (EC)) and physical properties (e.g., moisture content (MC), liquid limit (LL), plastic limit (PL), plasticity index (PI)) of the samples untreated and treated with the traditional and accelerated carbonated S/S processes were analyzed. Their variations on the depths of the soils were also studied. The result showed that the broad geotechnical properties of the soils, manifested in their PIs, were related to the concentration of the water soluble ions and in particular the free calcium ions. The samples treated with the accelerated carbonation technology (ACT), and the untreated samples contained limited number of free calcium ions in solutions and consequently interacted with waters in a similar way. Compared with the traditional cement-based S/S technology, e.g., treatment with ordinary portland cement (OPC) or EnvirOceM, ACT caused the increase of the PI of the treated soil and made it more stable during long-term weathering. The PI values for the four soils ascended according to the order: the EnvirOceM soil, the OPC soil, the ACT soil, and the untreated soil while their pH and EC values descended according to the same order.

'PERMIT' ion migration test for measuring the chloride ion transport of concrete on site

The ingress of chlorides into concrete is predominantly by the mechanism of diffusion and the resistance of concrete to the transport of chlorides is generally represented by its coefficient of diffusion. The determination of this coefficient normally requires long test duration (many months). Therefore, rapid test methods based on the electrical migration of ions have widely been used. The current procedure of chloride ion migration tests involves placing a concrete disc between an ion source solution and a neutral solution and accelerating the transport of ions from the source solution to the neutral solution by the application of a potential difference across the concrete disc. This means that, in order to determine the chloride transport resistance of concrete cover, cores should be extracted from the structure and tested in laboratories. In an attempt to facilitate testing of the concrete cover on site, an in situ ion migration test (hereafter referred to as PERMIT ion migration test for the unique identification of the new test) was developed. The PERMIT ion migration test was validated in the lab by carrying out a comparative investigation and correlating the results with the migration coefficient from the one-dimensional chloride migration test, the effective diffusion coefficient from the normal diffusion test and the apparent diffusion coefficient determined from chloride profiles. A range of concrete mixes made with ordinary Portland cement was used for this purpose. In addition, the effects of preferential flow of ions close to the concrete surface and the proximity of reinforcement within the test area on the in situ migration coefficients were investigated. It was observed that the in situ migration index, found in one working day, correlated well with the chloride diffusion coefficients from other tests. The quality of the surface layer of the cover concrete and the location of the reinforcement within the test area were found to affect the flow of ions through the concrete during the test. Based on the data, a procedure to carry out the PERMIT ion migration test was standardised.

Full-Scale Marine Exposure Tests on Treated and Untreated Concretes Initial 7-Year Results

An extensive chloride profiling program was undertaken on concrete pier stems erected in the vicinity of the Dornoch Bridge located at the Dornoch Firth in Northeast Scotland. The pier stems were 2 m (6.562 ft) high and octagonal in plan with 0.66 m (2.165 ft) wide faces. The piers were constructed in sets of three with the lowest of each set in the tidal zone and the highest in the atmospheric zone. The pier stems were placed in such a way that they would represent the exposure conditions of the actual bridge piers of the Dornoch Bridge. In all, six of the pier stems were made using plain ordinary portland cement (OPC) concrete (with three of these having the surface treated with silane); the remaining three pier stems had a concrete containing caltite as an additive. Three exposurezones were studied: the tidal zone, the splash zone, and the atmospheric zone. The tidal zone was further subdivided into two levels defined as low-level and high-level. Chloride profiles were obtained from the different regimes over a period of 7 years for all nine pier stems. This paper describes the nature of chloride ingress and the usefulness of diffusion parameters in classifying each exposure regimes. Furthermore, the effectiveness of silane and caltite in protecting concrete from chloride ingress in different exposure zones was studied.

Assessment of Self-Compacting Concrete Immersed in Acidic Solutions

Ettringite and thaumasite can be found among the deterioration products of cementitious materials exposed to sulfate and hydrochloric attack. The results of a test program to investigate the acid resistance of self-compacting concrete (SCC) and conventional concrete (CC), immersed up to 18 weeks at 20°C in sulfuric and hydrochloric acid solutions, are described. The SCC was prepared with 47% carboniferous limestone powder, as a replacement for cement, and an ordinary portland cement. The CC was prepared with portland cement only. The water-binder ratios of the SCC and CC were 0.36 and 0.46, respectively. The parameter investigated was the time, in weeks, taken to cause 10% mass loss of fully immersed concrete specimens in a 1% solution of sulfuric acid and the same amount of loss in a 1% solution of hydrochloric acid. The investigation indicated that the SCC performed better than the CC in sulfuric solution but was slightly more vulnerable to hydrochloric acid attack compared to CC. The mode of attack between the two solutions was different.

Carbonation and pH in Mortars Manufactured with Supplementary Cementitious Materials

An investigation of carbonation in mortars and methods of measuring the degree of carbonation and pH change is presented. The mortars were manufactured using ordinary portland cement, pulverized fuel ash, ground granulated blast-furnace slag, metakaolin, and microsilica. The mortars were exposed to a carbon dioxide-rich environment 5% CO2 to accelerate carbonation. The resulting carbonation was measured using phenolphthalein indicator and thermogravimetric analysis. The pH of the pore fluid and a powdered sample, extracted from the mortar, was measured to give an accurate indication of the actual pH of the concrete. The pH of the extracted powder mortar sample was found to be similar to the pH of the pore fluid expressed from the mortars. The thermogravimetric analysis suggested two distinct regions of transport of CO2 within mortar, a surface region where convection was prevalent and a deeper region where diffusion was dominant. The use of microsilica has been shown to decrease the rate of carbonation, while pulverized fuel ash and ground granulated blast-furnace slag have a detrimental effect on carbonation. Metakaolin has little effect on carbonation.

Effects of seawater-neutralised bauxite refinery residue on properties of concrete

Various industrial by-products, such as fly ash, ground granulated blast-furnace slag and silica fume, have been used in concrete to improve its properties. This also enables any environmental issues associated with their disposal. Another material that is available in large quantities and requiring alternative methods of disposal is the Bauxite Refinery Reside (BRR) from the Bayer process used to extract alumina from bauxite. As this is highly caustic and causes many health hazards, Virotec International Ltd. developed a patented technology to convert this into a material that can be used commercially, known as Bauxsol™, for various environmental remediation applications. This use is limited to small quantities of seawater-neutralised BRR and hence an investigation was carried out to establish its potential utilisation as a sand replacement material in concrete. In addition to fresh properties of concrete containing seawater-neutralised BRR up to 20% by mass of Portland cement, mechanical and durability properties were determined. These properties indicated that seawater-neutralised BRR can be used to replace natural sand up to 10% by mass of cement to improve the durability properties of concrete without detrimentally affecting their physical properties. Combining these beneficial effects with environmental remediation applications, it can be concluded that there are specific applications where concretes containing seawater-neutralised BRR could be used.

Chemical and mechanical stability of sodium sulfate activated slag after exposure to elevated temperature

The chemical and mechanical stability of slag activated with two different concentrations of sodium sulfate (Na₂SO₄) after exposure to elevated temperatures ranging from 200 to 800 °C with an increment of 200 °C has been examined. Compressive strengths and pH of the hardened pastes before and after the exposure were determined. The various decomposition phases formed were identified using X-ray diffraction, thermogravimetric analysis and scanning electron microscopy. The results indicated that Na₂SO₄ activated slag has a better resistance to the degradation caused by exposure to elevated temperature up to 600 °C than Portland cement system as its relative strengths are superior. The finer slag and higher Na₂SO₄ concentration gave better temperature resistance. Whilst the pH of the hardened pastes decreased with an increase in temperature, it still maintained a sufficiently high pH for the protection of reinforcing bar against corrosion.

Testing the effectiveness of commonly-used site curing regimes

A range of seven test methods was used to assess the effectiveness of curing on C30 and C50 Portland cement concretes. Curing was by formwork retention, wrapping in wet hessian or wrapping in polythene for periods of between one and seven days. Specimens from each mix were also subjected to both air and water storage.

Strength development of mortars containing ground granulated blast-furnace slag: Effect of curing temperature and determination of apparent activation energies

The strength development of mortars containing ground granulated blast-furnace slag (ggbs) and portland cement was investigated. Variables were the level of ggbs in the binder, water-binder ratio and curing temperature. All mortars gain strength more rapidly at higher temperatures and have a lower calculated ultimate strength. The early age strength is much more sensitive to temperature for higher levels of ground granulated blast-furnace slag. The calculated ultimate strength is affected to a similar degree for all ggbs levels and water-binder ratios, with only the curing temperature having a significant effect. Apparent activation energies were determined according to ASTM C1074 and were found to vary approximately linearly with ggbs level from 34 kJ/mol for portland cement mortars to around 60 kJ/mol for mortars containing 70% ggbs. The water-binder ratio appears to have little or no effect oil the apparent activation energy. (c) 2005 Elsevier Ltd. All rights reserved.