Whatever the weather

Weathering and extreme environments

The permanency of a stone building is not set in stone, as the building fights a war of attrition against droplets of moisture, crystals of salts, and the elements. Rebecca Wood speaks to Professor Christopher Hall about his high technology approach to understanding this constant assault.

ements, concrete, brick, stone and rock are ubiquitous materials in construction and in oilfield engineering, but until relatively recently not much was understood about their chemistry, particularly how they react to hostile environments and how they decay. Professor Christopher Hall, Director of the Materials Science and Engineering Centre based at Edinburgh University, has spent many years devoted to increasing knowledge in these fields, using advanced scientific instrumental methods such as atomic force microscopy and Raman spectroscopy. Hall, together with Paul Barnes from Birkbeck College, London, even pioneered a new synchrotron X-ray diffraction method of mapping materials spatially called TEDDI, or tomographic energy-dispersive diffraction imaging, in the late 1990s.

Inorganic materials, such as ceramics and stone, are heterogeneous and complex and change over time due to their interactions with their environment, giving a surface layer that is different to the interior. Synchrotron X-ray techniques developed by Hall and his colleagues make it possible to map the full 3D structure of relatively large samples, limited in size only by what can be transported to the synchrotron station. Using these techniques, Hall says he can enter deeply inside materials for which there are no other techniques available for providing this sort of spatial mapping. Mapping of the microstructure of the material includes determining the crystalline diffraction pattern that is to say the crystalline composition of a material, in 3D. In essence we are getting a diffraction pattern from a small well-defined volume element within the material, then we can

step that volume element through the material to get a 3D picture of how the diffraction pattern changes. The diffraction pattern is a direct signature of the chemical compounds, or in our case the minerals of the solid-state structure, explains Hall. These techniques have practical applications, and Hall studies limestone used in buildings. Mineralogically, limestone is extremely simple, and is normally composed of 99% CaCO3 (calcium carbonate) when freshly quarried. However, once used to construct a building and then exposed to the elements for say 100 years, changes in the composition take place. Sulphur pollution in the air produces a chemical reaction within the limestone, which converts the calcium carbonate to calcium sulphate, otherwise known as gypsum. This process has been slowly occurring at Kings College Chapel at

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Main image overleaf: Skara Brae, a Neolithic settlement in the Orkney Isles, UK, maintained by Historic Scotland, has been investigated to determine the cause of the rapid decay of the site. A combination of physical, mechanical and chemical methods have been used to thoroughly investigate the rock types present. House 7 at Skara Brae was studied as a site of rapid decay (left), and severe surface spalling can clearly be seen (right)

Cambridge University, and Hall has been able to map the distribution of gypsum behind the exposed face of the chapel wall. By removing a plug roughly the thickness of a whiteboard marker pen and examining it using TEDDI, Hall has observed that the gypsum layer sits a couple of millimetres behind the weather face and extends inwards. This is important to know, Hall highlights, because replacing one mineral with another may cause a volume change, which leads to stresses developing within the material. These stresses may lead to micro-cracks, which may spread and cause the front of the wall to spall off. So you get this characteristic delamination on the front of buildings, which is a sign of weathering, explains Hall. The good, the bad and the ugly Weathering of limestone is not always bad news, however. As Hall points out there is a bad scenario and a good scenario, and it is a matter of knowing under which circumstances each type of weathering occurs. We would very much like to know under which circumstances these sort of slow progressive chemical changes occur in a benign way, and in other cases where they occur catastrophically and cause loss of appearance or function, he stresses.

The heart of the issue, and the area of most fascination for Hall, is why these infinitesimal local changes do lead to stresses. It is not as clear cut as one change leading to one stress, he explains. In fact scientifically it is not at all obvious how this occurs, and discovering the mechanism is the subject of indepth research being carried out in my laboratory to try to measure the stress between two crystals. This stress is a general problem, but is also particularly applicable to stone decay. When push comes to shove Porous building materials such as limestone and sandstone absorb water when exposed to moisture in the form of rainwater or groundwater. The water which often contains dissolved salts is drawn into the material by capillary action and travels into natural voids in the matrix of the rock. When environmental conditions change, such as the weather becoming drier, or the move from winter into spring, the water evaporates in many cases leaving behind solid salts. In coastal environments, such as at the prehistoric site of Skara Brae in the Orkney Islands, UK, these salts are often sodium chloride. Commonly, in urban areas where the atmosphere is polluted sulphate salts are formed, which is the case at Kings College in Cambridge.

These solid salts grow in the pores and cavities of the stone, and as they grow inside the stone they come to the point where they fill the space available to them. If they grow further than this they develop stresses, which act against the particles in the rock and in many cases those stresses reach the point where they cause the rock to crack. It starts off with micro-cracks, which then join up and become significant visible damage where delamination may occur, and the surface of the stone may detach and fall off, says Hall. Scientifically, the question Hall would like an answer to from these observations is can we understand the origins of the stress caused by the crystals forming? What is driving the stress, can we measure it and eventually, can we control it? Controlling salt crystal damage to porous construction materials is an important issue, not just for conserving sites of cultural heritage, but also for preserving civil infrastructure. The salt stress process occurs in concrete and can cause the material to deteriorate in the surfaces of roads, airport runways, on bridges or motorway overpasses. There is a huge amount of concrete in the world and a lot of it is slowly deteriorating, often because of the crystallisation of salts within the body of the material, Hall explains.

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Together with Edinburgh University PhD student Andrea Hamilton, Hall is currently investigating salt crystal stresses by growing one crystal against a second, and then measuring the stress caused when the first crystal pushes the second out of the way. In another experiment, research fellow Vicky Pugsley grows crystals under controlled conditions and measures the bulging that occurs when a crystal keeps growing inside a cavity that is too small to contain it. Watching cement set Taking the research one step further, these techniques can also be used to track the chemical changes which occur

in cements during hardening and setting processes. With these techniques it is possible to follow in great detail how the minerals of the original cement are transformed by reaction with water to form the cohesive binding materials of the hardened cement. Of particular interest to Hall has been what happens at the relatively high temperatures encountered when cements are used in the construction of oil and gas wells. Here the cements are forced to work at over 100C. It is incredibly difficult to monitor the chemical changes that occur during the hydration of cement at such high temperatures, but by placing the cement in an autoclave cell, and bombarding it with the intense X-ray beam from a syn-

Research into how cement sets at high temperatures could help develop novel materials to line oil wells (Image: Schlumberger)

Keeping a weather-eye on ancient glass

The work carried out in Halls laboratory is not just concerned with concrete, cement, rocks and stone. Glass is another important building material that is subject to corrosion over time, and by learning more about the chemistry of glass corrosion it may be possible to optimise storage conditions for antique glass artefacts housed in the many museums around the world. In a joint PhD at the Centre for Materials Science and Engineering in Edinburgh, and the Laboratoire de Dynamique Interactions et Ractivit in France, Laurianne Robinet is working on the deterioration of antique glass in a project linked with the National Museums of Scotland. She is using Raman spectroscopy and secondary ion mass spectrometry to study the alteration of the surface layer of the glass. This effect called crizzling eventually produces fine cracking of the weathered surface and serious damage. The research has shown that the seemingly benign storage conditions of a typical wooden display case are in fact highly aggressive towards the ancient glass, which is less durable than modern glass compositions. The wood releases organic vapours such as formic acid, acetic acid and formaldehyde, which can attack the glass under humid conditions. Corrosion of glass is normally attributed to a two-stage reaction between the glass surface and atmospheric moisture. In a recent paper on the subject, Robinet explains that the first stage is an ion exchange process between penetrating H+ and/or H3O+ ions from the moisture and an alkali metal ion (typically Na+), which is removed from the glass. The rate of alkali extraction is diffusion-controlled and depends on the square root of time. At this stage, the silica network remains unchanged but a silica-rich film containing H2O forms on the glass surface. This film becomes increasingly alkaline and above pH9 the second stage occurs with decomposition of the silica network. The effects of the two reactions cannot be separated and occur simultaneously, normally with one dominating, resulting in both chemical and structural changes to the glass.

chrotron, it is possible to observe the cement setting under these conditions. As a development of this, Hall is now looking at the properties of some new so-called hydroceramics, made from mixtures of lime, silica, alumina and water. These form at temperatures of around 200-300C and have potential use as durable formulations for geothermal well construction. With research fellow Nicola Meller, Hall is currently exploring the use of microwaves to cure such systems, so in order to use the synchrotron methods to monitor the curing reactions, it is necessary to develop new autoclave cells that function at higher temperatures. This is currently the subject of an EPSRC-funded project. Without a doubt there are many facets to Halls high technology approach to understanding how porous materials behave in hostile environments, and some exciting new materials are the spoils of this war against the elements. Further reading
Water Transport in Brick, Stone and Concrete, Spon Press, 2002, Christopher Hall and William D Hoff.

Further information
For further information, contact Professor Christopher Hall, FIMMM, Director of Research, Centre for Materials Science and School of Engineering and Electronics, The University of Edinburgh, Sanderson Building, Kings Buildings, Edinburgh, EH9 3JL, UK. Tel: +44 (0)131 650 Ancient glass is more prone to deterioration than modern compositions (left). Crizzling can occur as shown in this close up (right). (Images: National Museums Scotland) 5679. E-mail: christopher.hall@ed.ac.uk. Website: www.cmse.ed.ac.uk.

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