Hannelore Derluyn

A Pore-Scale Study of Fracture Dynamics in Rock Using X-ray Micro-CT Under Ambient Freeze–Thaw Cycling

Freeze-thaw cycling stresses many environments which include porous media such as soil, rock and concrete. Climate change can expose new regions and subject others to a changing freeze-thaw frequency. Therefore, understanding and predicting the effect of freeze-thaw cycles is important in environmental science, the built environment and cultural heritage preservation. In this paper, we explore the possibilities of state-of-the-art micro-CT in studying the pore scale dynamics related to freezing and thawing. The experiments show the development of a fracture network in a porous limestone when cooling to -9.7 °C, at which an exothermal temperature peak is a proxy for ice crystallization. The dynamics of the fracture network are visualized with a time frame of 80 s. Theoretical assumptions predict that crystallization in these experiments occurs in pores of 6-20.1 nm under transient conditions. Here, the crystallization-induced stress exceeds rock strength when the local crystal fraction in the pores is 4.3%. The location of fractures is strongly related to preferential water uptake paths and rock texture, which are visually identified. Laboratory, continuous X-ray micro-CT scanning opens new perspectives for the pore-scale study of ice crystallization in porous media as well as for environmental processes related to freeze-thaw fracturing.

Metastability Limit for the Nucleation of NaCl Crystals in Confinement.

We study the spontaneous nucleation and growth of sodium chloride crystals induced by controlled evaporation in confined geometries (microcapillaries) spanning several orders of magnitude in volume. In all experiments, the nucleation happens reproducibly at a very high supersaturation S ∼ 1.6 and is independent of the size, shape, and surface properties of the microcapillary. We show from classical nucleation theory that this is expected: S ∼ 1.6 corresponds to the point where nucleation first becomes observable on experimental time scales. A consequence of the high supersaturations reached at the onset of nucleation is the very rapid growth of a single skeletal (Hopper) crystal. Experiments on porous media also reveal the formation of Hopper crystals in the entrapped liquid pockets in the porous network and consequently underline the fact that sodium chloride can easily reach high supersaturations, in spite of what is commonly assumed for this salt.

Characterizing saline uptake and salt distributions in porous limestone with neutron radiography and X-ray micro-tomography

Samples of Savonnières limestone subjected to repeated wetting–drying cycles were investigated by both neutron radiography and X-ray micro-tomography to collect information on saline uptake and salt precipitation. Capillary uptake of water, 1.4 molal sodium sulphate and 5.8 molal sodium chloride solution was visualized with neutron radiography. The liquid penetration coefficients and diffusivities were determined and are markedly lower for the salt solutions than for water, due to the higher surface tension and viscosity of salt solutions. Halite distributions were derived from neutron radiographs. Porosity analysis of X-ray tomographic datasets allowed quantifying thenardite distributions and porosity decrease due to salt crystallization.

Drying of salt contaminated porous media: Effect of primary and secondary nucleation

The drying of porous media is of major importance for civil engineering, geophysics, petrophysics, and the conservation of stone artworks and buildings. More often than not, stones contain salts that can be mobilized by water (e.g., rain) and crystallize during drying. The drying speed is strongly influenced by the crystallization of the salts, but its dynamics remains incompletely understood. Here, we report that the mechanisms of salt precipitation, specifically the primary or secondary nucleation, and the crystal growth are the key factors that determine the drying behaviour of salt contaminated porous materials and the physical weathering generated by salt crystallization. When the same amount of water is used to dissolve the salt present in a stone, depending on whether this is done by a rapid saturation with liquid water or by a slow saturation using water vapor, different evaporation kinetics and salt weathering due to different crystallization pathways are observed.

Data-fusion of high resolution X-ray CT, SEM and EDS for 3D and pseudo-3D chemical and structural characterization of sandstone

When dealing with the characterization of the structure and composition of natural stones, problems of representativeness and choice of analysis technique almost always occur. Since feature-sizes are typically spread over the nanometer to centimeter range, there is never one single technique that allows a rapid and complete characterization. Over the last few decades, high resolution X-ray CT (μ-CT) has become an invaluable tool for the 3D characterization of many materials, including natural stones. This technique has many important advantages, but there are also some limitations, including a tradeoff between resolution and sample size and a lack of chemical information. For geologists, this chemical information is of importance for the determination of minerals inside samples. We suggest a workflow for the complete chemical and structural characterization of a representative volume of a heterogeneous geological material. This workflow consists of combining information derived from CT scans at different spatial resolutions with information from scanning electron microscopy and energy-dispersive X-ray spectroscopy.

Hygroscopic Behavior of Paper and Books

This study presents experimental analysis and numerical modeling of hygroscopic moisture buffering by paper and books. First, a literature review of moisture transport properties of paper is presented. Experimental work on two paper types includes SEM analysis of the paper structure, determination of sorption isotherms and water vapor permeability measurements. A hysteretic model for paper is presented, which is based on the measurement of the main adsorption and desorption curves. It is shown that the water vapor permeability in a hysteretic model is dependent on the moisture content and not on the relative humidity. Books consist of several paper sheets with air layers between the sheets. To take the air layers into account, a parallel transport model is proposed to determine the effective moisture transport properties of books taking into account the air layers. The dynamic hygroscopic behavior of small book samples was measured. It is shown that, although the water vapor permeability of different paper types can be quite different, the effusivity of a book highly depends on the presence of the air layers and can therefore remain comparable for different paper types.

Multi-disciplinary characterization and monitoring of sandstone (Kandla Grey) under different external conditions

Nowadays there is an increase of imported natural building stones, often used as replacement of local, more traditional building stones. The durability of these traditional stones is generally well known; however, when new imported materials are used, it is essential to study their behaviour under the current and local climatological conditions to predict their weathering resistance. In addition to water exposure, these building materials have to be resistant to significant mechanical stress created by the imbibition of de-icing salt solutions, frequently used during winter in Western Europe, with temperature periodically changing from freeze to thaw conditions. Porous network modifications related to the materials’ chemical composition are very complex when different forces are acting on the stone itself. Therefore it is crucial to determine the internal structure of the building stone under changing external conditions with and without the presence of de-icing salts, to understand the influence of these additional salts. In this paper, particular attention was paid to the multi-characterization of compact Kandla Grey laminated sandstone, a building stone frequently imported from India to Belgium recently. Traditional as well as highly advanced research techniques were used for the characterization and monitoring of changes under different external conditions. This study demonstrates that the structural characteristics of the laminations have an effect on the frost resistance of the stone and its response to salt weathering. From the experiments carried out, it can be concluded that Kandla Grey can be sensitive to frost and salt weathering under the current climatic conditions in Western Europe.

Biogenic concrete protection driven by the formate oxidation by Methylocystis parvus OBBP

The effectiveness of Microbiologically Induced Carbonate Precipitation (MICP) from the formate oxidation by Methylocystis parvus OBBP as an alternative process for concrete protection was investigated. MICP was induced on Autoclaved Aerated Concrete (AAC), the model material, by immersing the material in 109 M. parvus cells mL−1 containing 5 g L−1 of calcium formate. A 2 days immersion of the material gave the maximum weight increase of the specimens (38 ± 19 mg) and this was likely due to the deposition of calcium carbonate, biomass, and unconverted calcium formate. The solid deposition mainly occurred in the micropores of the specimen, close to the outer surface. A significantly lower water absorption was observed in the bacterially treated specimens compared to the non-treated ones (up to 2.92 ± 0.91 kg m−2) and this could be attributed to the solid deposition. However, the sonication test demonstrated that the bacterial treatment did not give a consolidating effect to the material. Overall, compared to the currently employed urea hydrolysis process, the formate-based MICP by M. parvus offers a more environmentally friendly approach for the biotechnological application to protect concrete.

Texture and mineralogy influence on durability: The Macigno sandstone

The behaviour of ornamental stones in response to environmental changes or interactions is crucial when dealing with the conservation of cultural heritage. Weathering factors affect each rock differently, depending on structure, mineralogy, and extraction and implementation techniques. This work focuses on the Macigno sandstone, a dimension stone often employed in Tuscany over the centuries. A thorough mineralogical (optical microscopy, scanning electron microscopy and X-ray powder diffraction) and petrophysical characterization (i.e. mercury intrusion porosimetry, X-ray computed tomography, hygroscopic adsorption behaviour, ultrasounds, image analysis and capillary uptake) was made of the sandstone type extracted in the area of Greve in Chianti. The lithotype shows mineralogical (i.e. presence of mixed-layer phyllosilicates) and micro-porosimetric features, leading to a high susceptibility to relative humidity variation. Moreover, the influence of swelling minerals is related to weathering due to saline solution. The joint application of petrographic and petrophysical techniques allows an understanding of the characteristic weathering pattern of exfoliation (i.e. detachment of multiple thin stone layers, centimetre scale, that are sub-parallel to the stone surface).

Comparison between traditional laboratory tests, permeability measurements and CT-based fluid flow modelling for cultural heritage applications

In this paper, we examine the possibility to use on-site permeability measurements for cultural heritage applications as an alternative for traditional laboratory tests such as determination of the capillary absorption coefficient. These on-site measurements, performed with a portable air permeameter, were correlated with the pore network properties of eight sandstones and one granular limestone that are discussed in this paper. The network properties of the 9 materials tested in this study were obtained from micro-computed tomography (μCT) and compared to measurements and calculations of permeability and the capillary absorption rate of the stones under investigation, in order to find the correlation between pore network characteristics and fluid management characteristics of these sandstones. Results show a good correlation between capillary absorption, permeability and network properties, opening the possibility of using on-site permeability measurements as a standard method in cultural heritage applications.