Tuning Chemical and Morphological Properties of Ceria Nanopowders by Mechanochemistry.

Cerium oxide powders are widely used and are of fundamental importance in catalytic pollution control and energy production due to the unique chemical properties of CeO2. Processing steps involved in catalyst preparation, such as high-temperature calcination or mechanical milling processes, can alter the morphological and chemical properties of ceria, heavily affecting its final properties. Here, we focus on the tuning of CeO2 nanopowder properties by mild- and high-energy milling processes, as the mechanochemical synthesis is gaining increasing attention as a green synthesis method for catalyst production. The textural and redox properties were analyzed by an array of techniques to follow the aggregation and comminution mechanisms induced by mechanical stresses, which are more prominent under high-energy conditions but strongly depend on the starting properties of the ceria powders. Simultaneously, the evolution of surface defects and chemical properties was followed by Raman spectroscopy and H2 reduction tests, ultimately revealing a trade-off effect between structural and redox properties induced by the mechanochemical action. The mild-energy process appears to induce the largest enhancement in surface properties while maintaining bulk properties of the starting materials, hence confirming its effectiveness for its exploitation in catalysis.

Ceria-Zirconia Particles Wrapped in a 2D Carbon Envelope: Improved Low-Temperature Oxygen Transfer and Oxidation Activity.

Engineering the interface between different components of heterogeneous catalysts at nanometer level can radically alter their performances. This is particularly true for ceria-based catalysts where the interactions are critical for obtaining materials with enhanced properties. Here we show that mechanical contact achieved by high-energy milling of CeO2-ZrO2 powders and carbon soot results in the formation of a core of oxide particles wrapped in a thin carbon envelope. This 2D nanoscale carbon arrangement greatly increases the number and quality of contact points between the oxide and carbon. Consequently, the temperatures of activation and transfer of the oxygen in ceria are shifted to exceptionally low temperatures and the soot combustion rate is boosted. The study confirms the importance of the redox behavior of ceria-zirconia particles in the mechanism of soot oxidation and shows that the organization of contact points at the nanoscale can significantly modify the reactivity resulting in unexpected properties and functionalities.

Sintering Behaviour of Waste Olivine and Olivine/Alumina Blends.

The sintering behaviour of several green compacts made with olivine or olivine/alumina powder blends has been examined. To this goal, powders were attrition milled, uniaxially pressed into specimens and air sintered at temperatures ranging from 1100 to 1300 °C. The resulting samples were characterized by water absorption, shrinkage, phase composition and density. Compositions containing 5%, 10% and 20% Al2O3 have a sintering behaviour similar to that of olivine alone, reaching low residual porosity when fired at 1300 °C. Conversely, the composition containing 40% Al2O3 displays an almost flat shrinkage profile and maintains high residual porosity in the examined temperature range.

Fly and bottom ashes from biomass combustion as cement replacing components in mortars production: rheological behaviour of the pastes and materials compression strength.

In the present research mortar pastes obtained by replacing a commercial cement with the equivalent mass of 5, 10, 20 and 30 wt.% of fly ash or bottom ash from fir chips combustion, were prepared and rheologically characterized. It was observed that the presence of ash modifies their rheological behaviour with respect to the reference blend due to the presence, in the ashes, of KCl and K2SO4 which cause precipitation of gypsum and portlandite during the first hydration stages of the pastes. Hydrated materials containing 5 wt.% of ash display compression strength and absorption at 28 d of same magnitude as the reference composition; conversely, progressive increase of ash cause a continuous decline of materials performances. Conversely, samples tested after 180 d display a marked decline of compression strength, as a consequence of potassium elution and consequent alkali-silica reaction against materials under curing.

Steelmaking slag as aggregate for mortars: effects of particle dimension on compression strength.

The present paper reports on the results of some experiments obtained from the production, hydration and subsequent measurement of the mechanical properties of several mortars prepared using a commercial CII/B-LL Portland cement, steelmaking slag, superplasticizer and water. Relevant parameters for the mortar preparation are the weight ratios of cement/water, the weight ratio superplasticizer/cement and between fine and granulated coarse particles. It has been demonstrated that optimisation of such parameters leads to the production of materials with mechanical properties suitable for civil engineering applications. Moreover, materials with improved compressive strength can be prepared by the use of slag containing extensive amounts of large particles.

Possible production of ceramic tiles from marine dredging spoils alone and mixed with other waste materials.

Dredging spoils, due to their composition could be considered a new potential source for the production of monolithic ceramics. Nevertheless, abundance of coloured oxides in these materials preclude the possibility of obtaining white products, but not that of producing ceramics with a good mechanical behaviour. As goal of the present research we have produced and studied samples using not only dredging spoils alone, but also mixtures with other waste materials such as bottom ashes from an incinerator of municipal solid waste, incinerated seawage sludge from a municipal seawage treatment plant and steelworks slag. Blending of different components was done by attrition milling. Powders were pressed into specimens which were air sintered in a muffle furnace and their shrinkage on firing was determined. Water absorption, density, strength, hardness, fracture toughness, thermal expansion coefficient of the fired bodies were measured; XRD and SEM images were also examined. The fired samples were finally tested in acidic environment in order to evaluate their elution behaviour and consequently their environmental compatibility. It is observed that, although the shrinkage on firing is too high for the production of tiles, in all the compositions studied the sintering procedure leads to fine microstructures, good mechanical properties and to a limitation of the release of many of the most hazardous metals contained in the starting powders.