Study of the effectiveness of crystal growth modifiers in the prevention of damage due to crystallization of sodium carbonates in stone artworks

The disintegration of stone materials used in sculpture and architecture due to the crystallization of salts is capable of irreparably damaging artistic objects and historic buildings. A number of phosphonates and carboxylates were tested here as potential crystallization modifiers for sodium carbonate crystallization. Precipitated phases during crystallization induced either by cooling or by evaporation tests were nahcolite (NaHCO3), natron (Na2CO3∙10H2O) and thermonatrite (Na2CO3∙H2O), identified using X-ray diffraction. By using the thermodynamic code PHREEQC and the calculation of the nucleation rate it was demonstrated that nahcolite had to be first phase formed during both tests. The formation of the other phases depended on the experimental conditions under which the two tests were conducted. Nahcolite nucleation is strongly inhibited in the presence of sodium citrate tribasic dihydrate (CA), polyacrylic acid 2100MW (PA) and etidronic acid (HEDP), when the additives are dosed at appropriate concentrations and the pH range of the resulting solution is about 8. Electrostatic attraction generated between the deprotonated organic additives and the cations present in solution appears to be the principal mechanism of additive-nahcolite interaction. Salt weathering tests, in addition to mercury intrusion porosimetry tests allowed to quantify the damage induced by such salts. FESEM observation of both salts grown on calcite single crystals and in limestone blocks subjected to salt crystallization tests allowed to identify the effect of these additives on crystal growth and development. The results show that PA seems to be the best inhibitor, while CA and HEDP, which show similar behaviors, are slightly less effective. The use of such effective crystallization inhibitors may lead to more efficient preventive conservation of ornamental stone affected by crystallization damage due to formation of sodium carbonate crystals.

Reservoir characterization of the Cardium Formation in the Ferrier Oilfield, west-central Alberta, Canada.

This thesis has the main aim of defining the lithostratigraphy, depositional architecture, post-depositional modifications and reservoir characteristics of the Cardium Formation in the Ferrier Oilfield, and how these characteristics can have great impact over production rates, GOR and produced fluid discrimination. In the Ferrier area, the Cardium Formation is composed by a NE prograding clastic sequence made up of offshore to shoreface deposits sealed by marine shales. The main reservoir is composed by sandstones and conglomerates interpreted to have deposited in a shoreface depositional environment. Lithofacies and net reservoir thickness mapping led to more detailed understanding of the 3D reservoir architecture, and cross-sections shed light on the Cardium depositional architecture and post-deposition sediment erosion in the Ferrier area. Detailed core logging, thin section, SEM and CL analyses were used to study the mineralogy, texture and pore characterization of the Cardium reservoir, and three main compartments have been identified based on production data and reservoir characteristics. Finally, two situations showing odd production behaviour of the Cardium were resolved. This shed light on the effect of structural features and reservoir quality and thickness over hydrocarbon migration pathways. The Ferrier example offers a unique case of fluid discrimination in clastic reservoirs due both to depositional and post-depositional factors, and could be used as analogue for similar situations in the Western Canadian Sedimentary Basin.