Marijn Boone

4D imaging and quantification of pore structure modifications inside natural building stones by means of high resolution X-ray CT.

Weathering processes have been studied in detail for many natural building stones. The most commonly used analytical techniques in these studies are thin-section petrography, SEM, XRD and XRF. Most of these techniques are valuable for chemical and mineralogical analysis of the weathering patterns. However, to obtain crucial quantitative information on structural evolutions like porosity changes and growth of weathering crusts in function of time, non-destructive techniques become necessary. In this study, a Belgian historical calcareous sandstone, the Lede stone, was exposed to gaseous SO(2) under wet surface conditions according to the European Standard NBN EN 13919 (2003). Before, during and after the strong acid test, high resolution X-ray tomography has been performed to visualize gypsum crust formation to yield a better insight into the effects of gaseous SO(2) on the pore modification in 3D. The tomographic scans were taken at the Centre for X-ray Tomography at Ghent University (UGCT). With the aid of image analysis, partial porosity changes were calculated in different stadia of the process. Increasing porosity has been observed visually and quantitatively below the new superficial formed layer of gypsum crystals. In some cases micro-cracks and dissolution zones were detected on the grain boundaries of quartz. By using Morpho+, an in-house developed image analysis program, radial porosity, partial porosity, ratio of open and closed porosity and equivalent diameter of individual pore structures have been calculated. The results obtained in this study are promising for a better understanding of gypsum weathering mechanisms, porosity changes and patterns on natural building stones in four dimensions.

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.

High-Resolution X-Ray CT for 3D Petrography of Ferruginous Sandstone for an Investigation of Building Stone Decay

Diestian ferruginous sandstone has been used as the dominant building stone for monuments in the Hageland, a natural landscape in east‐central Belgium. Like all rocks, this stone type is sensitive to weathering. Case hardening was observed in combination with blackening of the exterior parts of the dressed stones. To determine the 3D petrography and to identify the structural differences between the exterior and interior parts, X‐ray computed tomography was used in combination with more traditional research techniques like optical microscopy and scanning electron microscopy. The 3D characterization of the ferruginous sandstone was performed with a high‐resolution X‐ray CT scanner (www.ugct.ugent.be) in combination with the flexible 3D analysis software Morpho+, which provides the necessary petrophysical parameters of the scanned samples in 3D. Besides providing the required 3D parameters like porosity, pore‐size distribution, grain size, grain orientation, and surface analysis, the results of the 3D analysis can also be visualized, which enables to understand and interpret the analysis results in a straightforward way. The complementarities between high‐quality X‐ray CT images and flexible 3D software and its relation with the more traditional microscopical research techniques are opening up new gateways in the study of weathering processes of natural building stones. Microsc. Res. Tech., 2011.

Real‐time visualization of Haines jumps in sandstone with laboratory‐based microcomputed tomography

In this work, we present a novel laboratory-based microcomputed tomography (micro-CT) experiment designed to investigate the pore-scale drainage behavior of natural sandstone under dynamic conditions. The fluid distribution in a Bentheimer sandstone was visualized every 4 s with a 12 s measurement time, allowing the investigation of single-pore and few-pore-filling events. To our knowledge, this is the first time that such measurements were performed outside of synchrotron facilities, illustrating the growing application potential of laboratory-based micro-CT with subminute temporal resolutions for geological research at the pore scale. To illustrate how the workflow can lead to an improved understanding of drainage behavior, the experiment was analyzed using a decomposition of the pore space into individual geometrical pores. Preliminary results from this analysis suggest that the distribution of drainage event sizes follows a power law scaling, as expected from percolation theory.

Holistic approach of pre-existing flaws on the decay of two limestones

This study aims to understand the influence of the microfacies and the determination of pre-existing flaws on the weathering behavior of two types of limestones. Therefore, both Lede and Noyant limestones were independently weathered by strong acid tests and freeze-thaw cycles. In order to characterize the weathering patterns inside the stones, a combination of high resolution X-ray CT, SEM-EDS and thin section microscopy was used. The advantage of high resolution X-ray CT is its non-destructive character and the obtained 3D structural information. By using this technique, a time-lapse sequence of the weathering patterns was obtained for both gypsum crust formation as well as crack formation due to freezing and thawing. This way, a clear link could be made with the initial non-weathered state. Thin section microscopy and SEM-EDS provided additional chemical information. The focus of this study lies in the processes that occur in the bioclast fragments in the stone and the influence of the surrounding cement or matrix. The results show that weathering patterns vary for both limestones although the causes of weathering were similar. In case of the Noyant stone, the weathering by crystallizing gypsum was mainly restricted to the microporous matrix of the stone, while in case of the Lede stone, several foraminifera and shell fragments were preferentially recrystallized. In general, the underlying microstructure determines the weathering pattern of the stone.

Monitoring of stainless-steel slag carbonation using X-ray computed microtomography

Steel production is one of the largest contributors to industrial CO2 emissions. This industry also generates large amounts of solid byproducts, such as slag and sludge. In this study, fine grained stainless-steel slag (SSS) is valorized to produce compacts with high compressive strength without the use of a hydraulic binder. This carbonation process is investigated on a pore-scale level to identify how the mineral phases in the SSS react with CO2, where carbonates are formed, and what the impact of these changes is on the pore network of the carbonated SSS compact. In addition to conventional research techniques, high-resolution X-ray computed tomography (HRXCT) is applied to visualize and quantify the changes in situ during the carbonation process. The results show that carbonates mainly precipitate at grain contacts and in capillary pores and this precipitation has little effect on the connectivity of the pore space. This paper also demonstrates the use of a custom-designed polymer reaction cell that allows in situ HRXCT analysis of the carbonation process. This shows the distribution and influence of water and CO2 in the pore network on the carbonate precipitation and, thus, the influence on the compressive strength development of the waste material.

Three-dimensional phase separation and identification in granite

Typical granite is mainly composed of quartz, plagioclase, and alkali feldspars, together with some smaller fractions of ferromagnesian phases and trace phases. The occurrence and abundance of these minerals can be determined by destructive methods, but the three-dimensional (3D) visualization of these mineral structures is very difficult. For geological samples, X-ray microcomputed tomography (mu CT) is a very powerful tool to visualize 3D structures. However, mu CT imaging is based on the X-ray linear attenuation coefficient, which depends on atomic composition, density, and X-ray energy, sometimes making it hard to identify different phases inside the sample. This problem can be overcome by combining mu CT with other techniques that provide chemical information. The combination of mu CT with micro-X-ray fluorescence (mu XRF) and X-ray diffraction (XRD) allows segmentation and identification of the different minerals at the surface of the sample. Combining this information with the 3D density model obtained through mu CT scanning of the granite allows 3D phase identification. In this paper the results of the analysis of a representative Precambrian granite by these three complementary techniques are discussed and combined with the results of more traditional techniques like thin-section petrography. Although the granite sample is shown to be very heterogeneous, correct phase identification in 3D is obtained.

Replacement stones for Lede stone in Belgian historical monuments

Abstract The Lede stone (Lutetian, Eocene) is an important historic building stone used in the NW of Belgium. In Ghent, it is dominant in the post-Romanesque built cultural heritage. Its use was restricted several times by socio-economic constraints. Since quarrying and production started to cease from the seventeenth century, periodic revivals favoured the use of Lede stone for new buildings and restoration projects. Sulphation is the main threat for the Lede stone as black crusts are the most common degradation phenomena on this arenaceous limestone. Around the turn of the nineteenth century, the Belgian Gobertange stone was the most widely used replacement material. Throughout the twentieth century, the use of replacement material shifted towards French limestones. However, their colour, texture and petrophysical properties differ from the Lede stone, for which a natural yellow–brown patina is very characteristic. In order to solve this mainly aesthetic issue, several new stone types are used as replacement stone in the twenty-first century, while many others have been suggested. It remains, however, difficult to find a replacement stone that matches the visual and petrophysical properties of the Lede stone. One remaining Lede stone quarry pit has increased its activity since 2011, offering the opportunity to use new Lede stone as replacement stone.

Laminar gypsum crust on lede stone: microspatial characterization and laboratory acid weathering

Gypsum crusts are typical decay forms on limestone in polluted urban environments. Their origin and relation to the stone facies have been thoroughly investigated in the past three decades. Here, we present the combined use of novel techniques for a microspatial structural, chemical and mechanical characterization of a laminar black gypsum crust on a sandy limestone. These techniques include i.a. X-ray computed microtomography, X-ray Fluorescence micromapping, permeability mapping and the scratch test. They reveal the typical architecture of a laminar gypsum crust, with an outer opaque layer, a subsurface gypsum crystallization layer and a deeper cracked zone passing irregularly into the sound stone. Gypsum crystallization is mostly restricted to an irregular outer zone with an average thickness of 500µm, while cracks are found deeper within the rock. These cracks decrease the rock strength to more than 27.5mm below the surface. Because of their surface parallel orientation and thickness of >10-100µm, they create the potential for surface scaling. This is shown by a laboratory acid test where the crack network extensively developed due to further exposure to an SO2 environment. The use of novel techniques opens potential for the study of different decay forms and can be used for stone diagnosis with regards to conservation studies.

Novel injectable, self-gelling hydrogel–microparticle composites for bone regeneration consisting of gellan gum and calcium and magnesium carbonate microparticles

The suitability of hydrogel biomaterials for bone regeneration can be improved by incorporation of an inorganic phase in particle form, thus maintaining hydrogel injectability. In this study, carbonate microparticles containing different amounts of calcium (Ca) and magnesium (Mg) were added to solutions of the anionic polysaccharide gellan gum (GG) to crosslink GG by release of Ca2+ and Mg2+ from microparticles and thereby induce formation of hydrogel-microparticle composites. It was hypothesized that increasing Mg content of microparticles would promote GG hydrogel formation. The effect of Mg incorporation on cytocompatibility and cell growth was also studied. Microparticles were formed by mixing Ca2+ and Mg2+ and [Formula: see text] ions in varying concentrations. Microparticles were characterized physiochemically and subsequently mixed with GG solution to form hydrogel-microparticle composites. The elemental Ca:Mg ratio in the mineral formed was similar to the Ca:Mg ratio of the ions added. In the absence of Mg, vaterite was formed. At low Mg content, magnesian calcite was formed. Increasing the Mg content further caused formation of amorphous mineral. Microparticles of vaterite and magnesium calcite did not induce GG hydrogel formation, but addition of Mg-richer amorphous microparticles induced gelation within 20 min. Microparticles were dispersed homogeneously in hydrogels. MG-63 osteoblast-like cells were cultured in eluate from hydrogel-microparticle composites and on the composites themselves. All composites were cytocompatible. Cell growth was highest on composites containing particles with an equimolar Ca:Mg ratio. In summary, carbonate microparticles containing a sufficient amount of Mg induced GG hydrogel formation, resulting in injectable, cytocompatible hydrogel-microparticle composites.