Skip to Main Content
Gold Open Access: This article is published under the terms of the CC-BY 3.0 license.

A brief history of the nature, use and technology of binders in ancient constructions and buildings is outlined, including the apparent chronological discontinuities related to technological developments. The skilled and clever use of mineral resources is at the base of the technical achievements related to architectural activities, from simple adobe to high-performance modern concrete. It is argued that among pre-industrial binders the Roman pozzolanic mortars were highly optimized materials, skillfully prepared and very durable. Their innovative use in architecture is one of the keys of the successful expansion of the Roman Empire. The role of mineralogy and mineral reactions is emphasized in terms of: (1) the preparation and manufacturing of the binding materials; (2) the hardening process and the development of the physical properties of the binder; and (3) the archaeometric reconstruction of the ancient materials.

1. Historical survey

Living in a sheltered place, permanently or temporarily, is a fundamental need of humans. Nevertheless, the use of natural materials to build shelter is not exclusive to humans: termite mounds, bird nests, beaver dams, and beehives are perfect examples of efficient architectural skills on the part of animals. According to Mike Ashby “the difference lies in the competence demonstrated by man in his extraordinary ability to expand and adapt that competence and development” (Ashby, 2013, p. 11). After dwelling in natural caves and an extensive period of preparation of temporary structures made of organic materials (skin, wood, leaf, etc.), the development of long-lasting architecture in human prehistory was based necessarily on the clever use of natural rocks and/or man-made binders (Wright, 2005).

1.1. In the beginning it was clay …

The use of clay-rich mud to plaster huts and floors is the most direct use of natural minerals to solidify surfaces and make them impermeable (Wright, 1983; Staubach, 2013). This follows from the physical properties of clay minerals (Brown and Brindley, 1980; Bailey, 1988) which exhibit a small particle size and a marked flat morphology derived from the layered crystal structure. Clays in excess water form colloidal suspensions, and the settled fractions possess ideal plastic properties, so that readily formable materials can be obtained easily by soaking dry clay minerals.

Clays (and loess in China) have been used since Neolithic times to plaster walls (inside and outside), to consolidate and smooth rough floors and eventually reshape them repeatedly after use, to waterproof roofs made of organic material, and eventually as a mortar between stones and, finally, mudbricks. There is ample evidence of this architectural use of clays in the Middle East starting from the 10th millennium BC (see for example Schmandt-Besserat, 1977). In its simplest form, with no use of pyrotechnology, a masonry wall can be composed of sun-dried bricks (adobe) bound by a moist layer of mud that, on drying, makes the wall a solid mass of dry clay (Artioli and Secco, 2016). In other cases earth-based structures are formed by direct application and shaping of the constructions: these techniques are variously referred to as cob, if they have a load-bearing role, or wattle and daub if the earth has an infilling role (Friesem et al., 2017). In some cases the clay slabs or blocks can be cut directly out of clay or muddy soil if they are naturally consolidated by organic material (turf, sod) or other pedogenetic processes (Huisman and Milek, 2017). The man-made clay bricks and the clay mortars regularly contain a substantial organic (straw, dung) or inorganic component (gravel, pebbles) in order to avoid cracking upon drying; a technology developed before or in parallel with pottery making. The past use of unfired or sunbaked clay products is often difficult to assess in the archaeological record, because they are subject to rapid degradation mainly by wind erosion, water and salts (Friesem et al., 2017). Only in rather arid climates are ancient occurrences still recognizable (Figs. 1, 2), in most cases as structures embedded in mounds (tells) formed by layers of sequential human activity.

Figure 1.

The massive body of the Deffufa (‘mud-brick building’ in Nubian) of Kerma, Nubia. It was built entirely of sun-dried bricks and was the reference structure of the classic Kush civilization (2000–1500 BC).

Figure 1.

The massive body of the Deffufa (‘mud-brick building’ in Nubian) of Kerma, Nubia. It was built entirely of sun-dried bricks and was the reference structure of the classic Kush civilization (2000–1500 BC).

Figure 2.

Mud-brick qubba in the cemetery from the Islamic period near Dongola, Sudan. Qubbas are domed mausoleums which contain the grave of a saint or some important personage.

Figure 2.

Mud-brick qubba in the cemetery from the Islamic period near Dongola, Sudan. Qubbas are domed mausoleums which contain the grave of a saint or some important personage.

The earliest evidence of the use of sun-dried bricks is reported from the Pre-Pottery Neolithic layers in Jericho, Israel (9th millennium BC: Kenyon, 1981), in Nemrik, Iraq (Kozlowski and Kempisty, 1990) and in Ganj Darreh, Iran (Vatandoust et al., 2011) at least from the 8th millennium BC. Evidence of the use of mudbricks in the Indus Valley (Harappa, Mohenjo-Daro) started at about the same time (end of the 8th millennium BC: Khan and Lemmen, 2013). Jericho stands as a special site combining the early systematic evidence of the use of mud-brick buildings alongside the earliest example of a Cyclopean structure, a massive round tower ~10 m in diameter and standing to almost the same height; though the significance of such massive construction is still debated (Kenyon, 1981; Bar-Yosef, 1986). There is ample use of mud-brick structures in the site of Çatalhöyük (7500–6000 BC: Hodder, 2006, 2012) and a number of other Anatolian sites, together with painted mud plaster covering internal and external structures, for both practical and symbolic purposes (Figs 3, 4). Interestingly, although there is evidence that the Çatalhöyük people could have used pyrotechnologically produced lime plaster, there is no firm evidence of it being employed. The wall surfaces as well as the interior floors of the structures at Çatalhöyük were carefully plastered and frequently re-plastered in time, but were coated in earthen plasters, which were supplemented by a thinner coat of local white marly clay (Kopelson, 1996; Arkun, 2003). The first Mesopotamian building in brick on a monumental scale occurred in the Tell Halaf period (5th millenium BC: Oates, 1990; Robson, 1996). Rectangular mould-based bricks were introduced in Mesopotamia at least from the 4th or 3rd millennium BC (Tell Braq, Syria: Oates, 1990; Halaf, Syria: Davidson and McKerrell, 1976), rapidly becoming decorated or inscribed.

Figure 3.

Sun-dried mud bricks with clay mortar in a Neolithic wall at Çatalhöyük, Turkey.

Figure 3.

Sun-dried mud bricks with clay mortar in a Neolithic wall at Çatalhöyük, Turkey.

Figure 4.

An internal wall of a living quarter in Çatalhöyük showing wall plastering and decorations.

Figure 4.

An internal wall of a living quarter in Çatalhöyük showing wall plastering and decorations.

The tradition of using earthen architecture based on a mixture of clay, water and straw is still largely present in many rural areas of the world (Figs 5, 6), the splendid multi-story Al Mihdar Mosque of Tarim, Yemen and the Mosque of Djenne, Mali being two amazing examples of earthen architectural achievements. The technological basis of modern earth constructions is very similar to that inferred from the prehistoric record (Oates, 1990). It is worth mentioning that several trends of contemporary architecture (earth architecture, sustainable architecture, bioarchitecture, etc.) actively propose the modern use of clays or consolidated clays as natural materials in buildings (Minke, 2012). Furthermore, in the field of modern and ancient earthen architecture there are many unresolved issues concerning earthen conservation, capacity building and dissemination of information for appropriate conservation interventions on historic buildings, settlements and archaeological sites composed of earthen materials (Avrami et al., 2008; Fratini et al., 2011). The Getty Conservation Institute (GCI) through its Earthen Architecture Initiative (EAI: www.getty.edu/conservation/our_projects/field_projects/earthen/overview.html), a long-term legacy of the past Terra project, is at the forefront of active research and education on the theme.

Figure 5.

Modern production of sun-dried bricks in Sudan.

Figure 5.

Modern production of sun-dried bricks in Sudan.

Figure 6.

Mud-brick walls in Sardinian houses. Traditional earthen architecture is preserved alongside to modern concrete building.

Figure 6.

Mud-brick walls in Sardinian houses. Traditional earthen architecture is preserved alongside to modern concrete building.

1.2. And then fire came …

The Sumerian, Babylonian, Assyrian and Hittite civilizations used sun-dried clay tablets widely for cuneiform inscriptions, which was the written system for most of the languages of the Mesopotamian region (Walker, 1987). Large archives of tablets are available starting from about the 4th millennium BC and they present a number of conservation problems because they are fragile and salt-loaded (Organ, 1961). Only a very small number of them were originally fired, often accidentally during destructive conflagrations, and these are the most stable ones. Paradoxically, high temperature helps their preservation, so that modern electrical heating up to 740°C seems to be one of the best conservation treatments to stabilize these materials (Thickett et al., 2002). By firing clay tablets at high temperature, conservators are now applying the long-known pyrotechnological process which has been the basis of production of clay figurines since Upper Palaeolithic times (see the Venus of Dolní Veštonice, Vandiver et al., 1989), the making of early fired ceramics in Eastern Asia since at least ~ 15000 y BC (Kuzmin, 2006; Wu et al., 2012; Gibbs, 2015), and the shift from sun-dried to fired bricks in Mesopotamia around the 3rd millennium BC. It is the very same firing process transforming plastic clays into stable structural products (Artioli, 2010; Heimann et al., 2010; Staubach, 2013): during firing the clay minerals are dehydroxylated progressively and reactive oxides are formed, yielding glass and a variety of high-temperature crystal phases, depending on the starting clay composition and the time-temperature path followed. High temperatures and long firing times imply more complete reactions, better crystallization and highly sintered micro-structures (Cultrone et al., 2004). Technically, fired bricks are ~15% denser than corresponding mudbricks of the same size, and about five times more resistant to compression. They are also lighter than natural limestone but possess almost doubled values of the compressive strength of many common carbonate stones. Bricks represent an almost ideal unit material for masonry.

Fired bricks bearing inscriptions (Fig. 7) have been found in most Middle Eastern excavations, including Babylonia (Oppenheim, 1965), Nimrud (Oates, 1961) and Nippur (McCown, 1952). The buildings in many of the Mesopotamian tells are made of mixed construction materials: mainly mudbricks, but also fired bricks and stones. In fact “…once bricks had been developed, it became general practice to build the mass of a building in sun-dried bricks, whilst facing the lower courses and paving the floors with kiln-fired bricks. In a country short of wood for fuel, baked bricks were a luxury, commonly used only where necessary to protect the unfired from erosion by wind or water.” (Moorey, 1999). The large prevalence of mudbricks may prove that “burnt bricks were not as fundamental to Mesopotamian civilization as was fine stone dressing to Pharaonic civilization” (Wright, 2005, p. 110). The culmination of burnt brick construction in Mesopotamia was during Neo-Babylonian times (see the famous Ishtar Gate and Processional Way at Babylon, which also represent a great example of glaze decoration of bricks). A Mesopotamian-type evolution of building techniques is present also in the Indus Valley, where the transition from mudbricks to fired bricks appears in the Kot-Dijan period (2800–2600 BC) and burnt bricks become common in the mature Harappan stage (2600–2450 BC; Kenoyer, 1991; Khan and Lemmen, 2013), used mostly with simple clay mortar (Mackay, 1938). There are no other known examples of structural use of fired bricks elsewhere in the world until the first half of the 1st millennium BC, whereas already in the 2nd millennium BC there is ample evidence of the use of terra-cottas for roofing tiles and temple decorations in Greece and later in Etruria. Roofing tiles were also introduced in China during the Shang Dinasty (1700–1027 BC, Sui Pheng, 2001).

Figure. 7.

Inscribed bricks in the wall of Chogha Zanbil, the great Elamite zigurrath in Iran, some 30 km south-east of Susa.

Figure. 7.

Inscribed bricks in the wall of Chogha Zanbil, the great Elamite zigurrath in Iran, some 30 km south-east of Susa.

It is puzzling to note that everywhere in the world the process of mudbrick firing for architectural purposes occurred several thousand years later than the use of pyrotechnology to fire lime and ceramics in the same regions. The production of fired bricks of course required large fuel resources and substantial manpower (Potts, 2014). In any case the bricks were used to produce more flexible architecture and more stable masonry, even if the brick units were not strengthened with binder. In Mesopotamia a mixture of gypsum and clay was mostly used as mortar, apparently following an interesting regional pattern (see fig. 14 of Kingery et al., 1988), although the lack of scientific analyses and the use of ambiguous terminology for materials makes many of the early archaeological reports rather unreliable (Moorey, 1999, p. 330). Note that some of the Mesopotamian buildings encompass the early known water-treatment structures (Sanizadeh, 2008): in several of them some degree of waterproofing was obtained by use of fired bricks and tar plastering. In Mesopotamia the first use of bitumen (or a mixture of gypsum and bitumen) as mortar in masonry is recorded (Moorey, 1999; Sauvage, 2011), as also reported by historical sources (Herodotus 1, 179, 1–4): “Further, I must relate where the earth was used as it was dug from the moat and how the wall was constructed. As they dug the moat, they made bricks of the earth which was carried out of the place they dug, and when they had moulded bricks enough, they baked them in ovens; then using hot bitumen for cement and interposing layers of wattled reeds at every thirtieth course of bricks, they built first the border of the moat and then the wall itself in the same fashion. … There is another city, called Is, eight days’ journey from Babylon, where there is a little river, also named Is, a tributary of the Euphrates river; from the source of this river Is, many lumps of bitumen rise with the water; and from there the bitumen was brought for the wall of Babylon.” The latter phrase of Herodotus indicates how common the tar material was in the area.

2. Classification of inorganic binders: their chemistry and mineralogy

Before delving into the details of binder developments through prehistory and history, it is necessary to summarize the nature and properties of the materials. Because of the ample literature available (Barnes and Bensted, 2002; Hewlett, 2003; Artioli, 2010), only a brief introduction will be given.

To avoid confusion, we will define the terms used for the binding materials following the physical condition and context of use (Hobbs and Siddall, 2011). ‘Cement’ is a powder material providing internal cohesion derived from some sort of chemical reaction, mostly with water; ‘concrete’ is a composite made by a binder and large-sized (inert) aggregate material; ‘mortar’ is a composite made by a binder and small-sized aggregate material, mostly used as structural binder between masonry units (bricks, stones); ‘plaster’ is any mortar or binder material used for wall and floor covering, mainly for smoothing, waterproofing, or preparation for paintings and decorations.

Cements based on Portland-type clinkers, mortars (pastes and plasters prepared with fine aggregates) and other inorganic binders form an important class of construction material: they are all supplied as powders and when mixed with water they form a fluid mass (paste) that can be shaped, moulded, added to other components or attached to the surface of other materials. The paste then hardens spontaneously under normal environmental conditions. Binding materials are used in buildings with the aim of (1) making structural elements for constructions; (2) increasing the resistance of the construction by linking the structural and architectural elements; (3) increasing waterproofing and protecting masonry surfaces from environmental degradation; and (4) preparing substrates for artwork and decorative purposes.

Excluding the tar products mentioned above and binders and adhesives based on polymeric compounds, virtually all binders used in antiquity were based on carbonates (calcite, dolomite), sulfates (gypsum) or alumino-silicates (cements). Table 1 provides an overall classification of inorganic binders based on their chemical nature and the main reaction process when mixed with water. The important concept is that in all cases the pyrotechnological production process yields a reactive material that transforms into a more stable product during setting and hardening. The major differences between the different binder types are: (1) the nature of the starting material that determines the chemical reaction pathway; and (2) the temperature of the firing process that controls the quality and reactivity of the starting binder.

Table 1.

Main types of inorganic binders, their nature and reaction processes.

Type of binderStarting materialAppx. T of firing (°C)Reactive material productReaction process
Binders based on carbonateLime plasterlimestone800–1000Quicklime (CaO) Slaked lime (Ca(OH)2)aerial carbonation
Hydraulic Lime plasterlimestoneSlaked lime + pozzolanpozzolanic reaction
Natural Hydraulic Lime plasterlimestone + clays/volcanic glassNatural hydraulic limehydration reaction
Magnesian plasterdolomiteSlaked magnesia-lime (Ca(OH)2) (Mg(OH)2)aerial carbonation
Binders based on gypsumGypsum plaster (Plaster of Paris)gypsum250–300Bassanite CaSO4·0.5H2Ohydration
Binders based on Portland clinkerPortland clinker (cement)limestone + clays/marls1400–1450Clinker phases (alite C3S, belite C2S, Ca-aluminate C3A)cement hydration
Type of binderStarting materialAppx. T of firing (°C)Reactive material productReaction process
Binders based on carbonateLime plasterlimestone800–1000Quicklime (CaO) Slaked lime (Ca(OH)2)aerial carbonation
Hydraulic Lime plasterlimestoneSlaked lime + pozzolanpozzolanic reaction
Natural Hydraulic Lime plasterlimestone + clays/volcanic glassNatural hydraulic limehydration reaction
Magnesian plasterdolomiteSlaked magnesia-lime (Ca(OH)2) (Mg(OH)2)aerial carbonation
Binders based on gypsumGypsum plaster (Plaster of Paris)gypsum250–300Bassanite CaSO4·0.5H2Ohydration
Binders based on Portland clinkerPortland clinker (cement)limestone + clays/marls1400–1450Clinker phases (alite C3S, belite C2S, Ca-aluminate C3A)cement hydration

Furthermore, a fundamental difference concerning the nature of the reaction processes of lime-saturated binders is whether they involve simple absorption of CO2 from the gas phase to produce carbonates (aerial carbonation), or whether they also involve more complex processes of dissolution of alumino-silicate phases and precipitation of hydrated calcium-aluminium-silicate phases (‘pozzolanic’ reactions). The former are known as aerial binders, because they set in contact with the atmosphere. The latter are called hydraulic binders, because they may harden even under water.

In practical terms, if the binder is used as produced from the kiln with adequate grinding, then the binder/water mixture is called ‘paste’, i.e. the whole volume of the mixture comprises reactive phases and it will convert finally into a material composed entirely of the recrystallized reaction products. Therefore, if a lime paste undergoes complete aerial carbonation it will end up as a material composed totally of fine calcite crystals. A magnesian lime paste will yield a material composed of calcium carbonate and magnesium carbonate. The re-hydration of a bassanite paste will produce a plaster composed totally of gypsum. Finally the complete hydration of a clinker should yield a material composed largely of Ca-Si-hydrates (C-S-H) and calcite (from the carbonation of excess portlandite). As may be suspected, it is the recrystallization of the reaction products in the matrix and the entanglement of the crystals of the newly formed phases that confers mechanical resistance to the mature binder. The microstructure (i.e. the size, shape and orientation of the crystal phases) of the binder thus fundamentally controls the physical and engineering properties of the material.

In practice, the reaction normally goes to completion for gypsum and lime plasters; the reactions of these processes are kinetically quite fast at ambient conditions. However, it is often found that the kinetics of magnesian plasters are much slower, so that reaction products (MgO and Mg(OH)2) are commonly present quite some time after the application. In the case of Portland cement, the hydration reaction barely goes to completion, so that a substantial part of the starting phases is invariably present with the reaction products even a long time after the mixture has been prepared.

Pure binder pastes are used rarely. It is much more common to mix part of the binder with a nominally unreactive phase (the so-called inert phase, or aggregate) such as quartz, in order to reduce volume changes during hardening and thus limit shrinkage effects. The role of the aggregate is to reduce macro-cracking during drying of the binder/water mixture, to increase the bulk modulus of the composite, and to increase the overall volume of the binder. If the aggregate is added with particle size in the sand range (generally referred to a standard with grain size in the range 0.6–0.8 mm), then the binder/aggregate/water mixture is called ‘mortar’. Depending on the mineral nature of the binder, we may have lime mortars, natural hydraulic lime mortars, magnesian lime mortars, gypsum mortars, or clinker mortars. Lime mortars and gypsum mortars are the materials mostly found in the archaeological and historical record. They are still much used for small-volume applications such as decorations, panels, wall plastering and repointing.

In the case of Portland clinker, which is used as the main material in large-scale applications, there is need of large-volume aggregates in the size range of coarse sand or pebbles. The cement/large aggregate/water mixture is called ‘concrete’. In most cases the various size fractions of the aggregates from fine to coarse are planned carefully through gradation models (following Bolomey, Fuller, Graf or Rissel curves; Day, 2003; Collepardi et al., 2007) in order to produce an optimal volume packing of the particles in the mix. The planning of the optimal quantities and sizes of cement, aggregate and water is defined ‘concrete mix design’.

3. The composition and properties of ancient mortars

3.1. Lime-based binders, technology and development

The first artificial binders used by mankind are the limestone- and gypsum-based plasters used widely in the Near and Middle East in the 7th and 8th millennia BC (Frierman, 1971; Gourdin and Kingery, 1975; Kingery et al., 1988). The technological basis of plaster material is very simple: the reactive compound (quicklime in the case of lime plasters) is obtained by burning limestone at the appropriate temperature (Table 1). Then the heated block is ground to a fine powder and slaked with water to form a slurry (at high water/solid ratio) or a paste (at low water/solid ratio) composed of portlandite (calcium hydroxide, Ca(OH)2). In Roman times long aging of the slaked slurry in excess water was a priority with respect to the modern attitude of using the ground powder and mixing it with water into a paste at the time of application. The effect of aging on the properties of the lime putty has been investigated thoroughly (Rodriguez-Navarro et al., 1998; Cazalla et al., 2000), as the issue is relevant for the preparation of restoration lime mortars (Ruiz-Agudo and Rodriguez-Navarro, 2009).

The reactions involved in the production and use of lime are:

 

CaCO3(calcite)+heatCaO(lime)+CO2(carbon dioxide)[production of quicklime]CaO(lime)+H2O(water)Ca(OH)2(Portlandite)+heat[quick hydration]Ca(OH)2+CO2CaCO3+H2O[long term carbonation]

The temperature needed to produce CaO should be ~850°C (Rodriguez-Navarro et al., 2009), though the decomposition reaction of the carbonate can also proceed at slightly lower temperatures (780–800°C) in reducing conditions. Operational temperatures of lime-kilns are in the range 920–1000°C in order to speed up the decarbonation reaction. Excessive temperatures are avoided because they produce unreactive‘dead-burned’ lime. The production of lime therefore is a very energyintensive process and it requires a substantial amount of biomass fuel. It has been estimated that the ratio of fuel biomass/quicklime is in the range 2–5 (Kingery et al., 1992; Hauptmann and Yalcin, 2001), so that about 4–8 tons of wood would be required to produce the quicklime necessary for one house. Considering the diffusion of lime plaster resulting from the excavations in the Levant, the production of lime could have had a serious impact on the environment (Rollefson and Kohler-Rollefson, 1992; Redman, 1999). Similar claims were raised for the Mayan Lowlands (Wernecke, 2008).

Traditionally, the burning of carbonates (limestones, dolomites, travertine, marbles, but also shells and corals) is performed in lime-kilns, which are massive furnaces sometimes several metres high, charged from above with decimetre- to metre-sized blocks of limestone, and then fired for days by adding wood or charcoal to the combustion chamber at the base (Oates, 1998; Williams, 2004). Several ancient limekilns have been excavated from Roman (Dix, 1982; Coulson and Wilkie, 1986), to Late Classic Maya (Abrams and Freter, 1996), to more recent times (Williams, 2004). A detailed description of lime burning operations in Roman times was supplied by Marcus Porcius Cato (Cato the Elder: On Agriculture, XXXVIII).

The fired blocks are then ground to obtain the fine powdered quicklime that is, however, rather unstable in normal humidity conditions and tends to hydrate quickly to portlandite. If the CaO powder is mixed with an exact (i.e. stoichiometric) amount of water (lime/water = 75.7/24.3 = 3.12 by weight) the product is a fine dry powder and the process is called ‘dry hydration’ because there is exactly the right amount of water required to produce portlandite. If the CaO powder is mixed with excess water then a smooth paste is obtained in a slurry form, and the process is referred to as ‘lime slaking’. The portlandite paste (slaked lime or lime putty) can then be used as a binder and an architectural component (filler, adhesive, cracks sealer, floor consolidant, surface smoother, etc.) or as a raw material for modelling objects, vessels and even artwork. After the application the paste dehydrates slowly and reacts with atmospheric CO2 producing a hard material composed of microcrystalline calcite. The kinetics of carbonation are slow (Van Balen, 2005) so that in recent samples the reaction is not complete and residual crystals of portlandite may be observed.

The quality of the binder depends on a variety of parameters, including the composition, porosity and impurity content of the fired limestone, the maximum temperature and the time–temperature path of the firing, and the conditions of slaking. The starting limestone should have a non-carbonate mineral content (usually silicates and clays) of <5 – 10 wt.%, and the carbonate should be pure calcium. If the carbonate contains flints or a substantial amount of clays, then some (alumino)-silicate reactive phases may form at high temperature, the material acquires hydraulic properties, and it is called natural hydraulic lime (NHL). This material will be discussed later. If the carbonate contains magnesium, derived from the presence of magnesian calcite (Ca1-xMgxCO3 with x < 0.1) or dolomite (CaMg(CO3)2), then the material is a magnesian- or dolomitic-lime (Table 1). The periclase (MgO) produced together with lime during firing has much slower rehydration kinetics with respect to CaO, so that in the magnesian putty both periclase and brucite (Mg(OH)2) are present together with portlandite (Blauer-Bohm and Jagers, 1997).

During carbonation and hardening the microstructure of the slaked lime paste changes significantly (Leslie and Hughes, 2002; Arandigoyen et al., 2006). The identification of lime-derived calcite from an unconsolidated archaeological layer of ground calcite therefore is essentially based on the carbonate particles’ dimensions (in the range 0.1–2.0 mm), its texture, and its mechanical properties (Kingery et al., 1988; Affonso and Freiberg, 2001; Karkanas, 2007). Optical microscopy (Fig. 8) is therefore a very useful tool to investigate the nature and texture of ancient lime mortars (Elsen, 2006; Pecchioni et al., 2014), although it may prove difficult to discriminate between fine-grained calcite of geological origin (chemically precipitated) and that derived from portlandite.

Figure 8.

Optical micrograph of the thin section of a Medieval lime mortar from the Sachuidic castle, Friuli, Italy. The images in plane polarized light (a) and cross polarized light (b) show fragments of geological carbonate, lime lumps and the lime binder matrix.

Figure 8.

Optical micrograph of the thin section of a Medieval lime mortar from the Sachuidic castle, Friuli, Italy. The images in plane polarized light (a) and cross polarized light (b) show fragments of geological carbonate, lime lumps and the lime binder matrix.

The presence and role of calcite nodules in the mortar (the so-called ‘lime lumps’) have been the subject of ample discussion, because of their importance in identifying ancient mortars (Hughes et al., 2001; Karkanas, 2007), in the quantitative determination of the original binder/aggregate proportions (Lindqvist and Sandström, 2000; Elsen, 2004), and in the protocols sometimes employed for radiocarbon dating (Pesce et al., 2012). In general, we may summarize that calcite nodules in the binder may have originated in one of three ways: as residues of unburned geological carbonate, as inhomogeneously slaked lime putty forming portlandite lumps that underwent late carbonation, or as reprecipitated late calcite. Failure to identify the proper nature of the lumps may lead to serious errors in the interpretation of the material and eventually in radiocarbon dating of the inappropriate fraction of the binder.

Very careful Fourier transform infrared spectroscopy (FTIR) work, based on the ratios of specific absorption peaks of calcite (specifically the ratio between in-plane and out-ofplane bending modes of the carbonate group), has been proposed as a technique to discriminate lime derived-calcite from natural calcite (Chu et al., 2008; Regev et al., 2010b). This discrimination may also be done using the luminescence properties of calcium carbonate (Machel et al., 1991; El Ali et al., 1993), as shown in the example of Fig. 9. Both methods rely on the different density and distribution of atomic defects in the calcite crystal structure. In principle the fractionation of carbon and oxygen stable isotopes during portlandite carbonation could also be used to test the nature of the carbonate phase (Ambers, 1987; van Strydonck et al., 1989; Kosednar-Legenstein et al., 2008). Once more, the issue is especially important when characterizing the carbonate fraction for radiocarbon dating of the mortar. In many cases the presence of ‘anthropogenic‘ (i.e. man-made) carbonate is identified through micromorphological features (Stoops et al., 2017), or by textural elements such as clear smooth surfaces representing the floor used, sometimes with a finishing coating (Affonso and Freiberg, 2001; Shahack-Gross et al., 2005; Karkanas, 2007; Karkanas and Goldberg, 2007).

Figure 9.

Cathodoluminescence image of a mortar showing sub-mm grains of geological carbonate embedded in the mortar binder.

Figure 9.

Cathodoluminescence image of a mortar showing sub-mm grains of geological carbonate embedded in the mortar binder.

The earliest well characterized example of quicklime production is the Hayonim Cave in Israel (Kingery et al., 1988; Goldberg and Bar-Yosef, 1998), dated to the Natufian period at ~10.4–10.0 ky BC. Numerous other reports of lime-plaster in the Pre-Pottery Neolithic sites of the Levant (8.7–7.0 ky BC) were reviewed and characterized carefully by Kingery and co-workers (1988). They demonstrated beyond any doubt that there was a widespread use of pyrotechnologically produced lime-based plaster in the Near East coastal area from Palestine to Anatolia (Thuesen and Gwozdz, 1982; Garfinkel, 1987; Malinowski and Garfinkel, 1991; Poduska et al., 2012). Especially striking are the plastered faces from ‘Ain Ghazal in Jordan, originally modelled on human skulls (Griffin et al., 1998), and the exceptional sculptured head found in Jericho (fig. 10 of Kingery et al., 1988; Goren et al., 2001) and Yiftahel (Milevski et al., 2008).

Figure 10.

The partially reconstructed Throne Room of King Minos in Knossos, Crete showing the ample use of lime plaster for wall decorations.

Figure 10.

The partially reconstructed Throne Room of King Minos in Knossos, Crete showing the ample use of lime plaster for wall decorations.

There are numerous interesting issues concerning the prehistoric development of lime-based binders in the Pre-Pottery Neolithic of the Levant. In the first place, as already mentioned, it is curious that limestone firing and production of reactive quicklime pre-dates ceramic pyrotechnology (Frierman, 1971), although this gap is now being partially revisited (Biton et al., 2014). Further, the plasters in this early phase “do not comprise the rendering of the floor, they are the floor itself” (Wright, 2005, p. 157), i.e. they are made as durable surfaces supporting loads and meant to be cleaned. They also rapidly extended to walls for protection and decoration (Fig. 4). It is evident, however, that at least several thousand years separate this early burst in the use of lime binders from any structural use connected with fired bricks in the region. Actually, there seems to be a puzzling discontinuity between this widespread use of lime plaster in the 8th and 7th millennia BC in the Levant (especially in skull-plastering, figurine modelling and floor plastering), and the subsequent evidence of use of lime in architecture in the 2nd millennium BC.

The case of Lepenski Vir, a small Neolithic village on the banks of the Danube, stands as an isolated example apparently unconnected with the previous Levantine experience and the subsequent reprise of lime plaster in the Minoan world. In Lepenski Vir a large number of peculiar trapezoidal huts have been excavated, each with a thick floor of red-coloured limestone plaster (Srejović, 1972, 1981; Radovanović, 2000; one XRD analysis of a Lepenski Vir sample is reported by Thuesen and Gwozdz, 1982). The settlement has been radiocarbon dated to the Early Neolithic (6200–5400 BC), though there are claims of early Mesolithic occupation (Radovanović, 1996; Boric, 2002; Bonsall et al., 2008). Despite the uncertainty in the early life-span of the village and nearby settlements (Vlasac, Padina and Hajdutka Vodenica), the question of interest to us is whether the lime pyrotechnology on the Danube has anything to do to the previous Levant experience, or rather is a stand-alone development of lime production. Carefully contextualized investigations are needed to clarify the problem. The report of the use of lime at Makri, Thrace and at the Drakaina Cave, Kefallonia, Ionian Islands in the 6th millennium BC (Karkanas, 2007; Karkanas and Stratouli, 2008; Karkanas and Efstratiou, 2009) may prove to be an interesting link between the Levant and the Serbian lime experiences.

After the Lepenski Vir case, there were some four thousand years of technological discontinuity, or maybe lack of archaeological information. Chronologically, the successive occurrences of lime mortars and lime plasters are in the Minoan world (2nd millennium BC), where lime-based materials were used extensively in Crete, Cyprus and elsewhere for wall decorations and cistern waterproofing (Shaw, 1973; Wright, 2005). Without dwelling on the details too much, extensive lime plastering in the walls has been found, mainly to cover rough wall surfaces and floors, leaving the smooth ashlar unplastered. Plasters covering wall surfaces have a fine lime finish or wash as they serve as support for the famous Palatial paintings (i.e. Knossos, Fig. 10) and decorations. They are always lime-based, even when the wall-building stones are rock gypsum (Cameron et al., 1977; Zoppi et al., 2012). We stress that no hard evidence is observed in this period of the use of lime mortar as a structural component (i.e. to strengthen the masonry or ashlar blocks): all the Minoan, Mycenean and the later Classical Greek ashlar is dry.

A key development occurring in the Greek world is the consistent and systematic use of pozzolanic material (volcanic ash, i.e. ‘Santorini earth’, or crushed ceramics, i.e. ‘cocciopesto’) replacing inert aggregate in the mortar used for waterproofing cisterns and waterways in Bronze Age Crete and Cyprus (Maravelaki-Kalaitzaki et al., 2003; Moropoulou et al., 2005; Theodoridou et al., 2013). The tradition continued in pre-Roman Rhodes (Koui and Ftikos, 1998). The later use in Laurion, Greece (4th century BC) of a very peculiar waterproofing layer obtained by mixing Pb-rich oxides (litharge) and Fe, Mn-rich ores with lime is also reported (Papadimitriou and Kordatos, 1993). This special occurrence is related to the mining and treatment of Pb-rich ores in the nearby mines, though it is difficult to define whether the layer investigated is a deposit developed as a byproduct of the ore processing or the conscious recycling of litharge slags during plaster manufacture.

As we will discuss, the reported occurrences bear two important consequences: (1) there is evidence of the appropriate use of hydraulic mortars and pozzolanic reactions in the Mediterranean area well before the Roman world; and (2) there is no firm evidence of the structural use of lime mortars in constructions (i.e. as a binder among masonry units) before the second half of the 1st millennium BC, except maybe the very early use of hot bitumen, discussed earlier, within the Mesopotamian context.

Outside the Mediterranean world, there is hardly any evidence for the use of lime plaster prior to the late 2nd millennium BC (Carran et al., 2012).

No evidence is reported on the early use of plaster or mortar in the pueblo cultures of the US south west or in the South American Andean world, where the Inca’s massive constructions of polygonal stones were assembled by smoothing the edges to make close contacts (Hyslop, 2014). Limited use of lime mortar, sometimes mixed with bitumen, has been reported at Machu Picchu (1450–1550 AD), though direct accounts and analyses are scarce (Prescott, 1847). In Central America the use of lime plaster is reported in Preclassical and Classical Central Mexico, and from the Classical Maya period (Hyman, 1970; Magaloni et al., 1995; Abrams and Freter, 1996; Hansen et al., 1997; Barba et al., 2009). Some of the earlier examples are the plastered platforms at Cuello, Belize (1100–600 BC) and Nakbè, Guatemala (900–600 BC; Villaseor Alonso, 2009). In Mayan monuments the use of lime is structural, although spectacular use was made of lime as substrate to paintings and frieze decoration. Magnesian lime plasters were also extensively used (Villaseor and Price, 2008). An early use of pumices as lightweight aggregate in poured lime mortar is reported for the roof slab of Building Y in the El Tajin site, the sacred city of the Totonac people (850–1100 BC; Rivera-Villareal and Krayer, 1996).

Interestingly, there is ample evidence that in Mesoamerica the lime plaster was prepared by mixing different kinds of organic materials such as honey or juice extracted from a number of local plants such as cactus (nopal juice, Opuntia ficus indica; Littmann, 1957, 1960; Laws, 1962; Magaloni et al., 1995). The type and extent of the effect of the organic molecules on the putty is still debated (Chandra et al., 1998; Bensted, 1999; Rodriguez-Navarro et al., 2017). On one hand there are claims that the organics destabilize portlandite chemically and release Ca ions, thus promoting pozzolanic reactions with impurity phases. On the other hand the physical effect of packing is emphasized, with the claim that the organics help the development of a more homogeneous microstructure, with smaller portlandite crystals, and ultimately a greater mechanical strength. The debate is open.

In China, there are accounts of the early use of lime during the Shang (1700–1027 BC) and the Zhou (1046–771 BC) Dynasties, the lime being mixed with sand and loess for wall facing and flooring. The palace site of Xianyang, Shaanxi province (350 BC) had the floors prepared with a mixture of lime, stone and pig’s blood (Yang et al., 2009) to give a dark red colour. The mortar formulation comprised lime, loess and sand; it became known as ‘tabia’ and became the regular material in use during the Eastern Tsin Dynasty (317–420 AD; Yang et al., 2009). Lime-based mortars were used extensively in ancient architecture, with examples reported in the Qiantan River dam, Dutifulness Monument, Sticky Rice Bridge and others, completed mainly before the Ming (AD 1368–1644) and the Qing dynasties (AD 1644–1911; Huang, 2003; Yu and Chen, 2004; Zeng et al., 2008). According to written sources (Song and KaiWu, 1982) lime-plaster production followed a traditional standard formula mixing lime and sticky rice solution up to 15–20 wt.%, and today the plaster is reported to be still in very good condition. Sticky rice is a type of rice grown in southeast and east Asia and it is composed mainly of amylopectin. Again, it seems that the organics influence the calcite dimensions and growth kinetics during carbonation (Zeng et al., 2008). A variety of organic substances has been reported to have been used in traditional Chinese mortar recipes (Fang et al., 2014; Zhang et al., 2014; Zhao et al., 2015), used both in masonry and in wooden buildings (Rao et al., 2015).

The greater Indian region had a very early start with the use of mud and bitumen mortars (referred to as ‘vajralepa’ mortar; Kumar, 1984; Reza, 2008) related to the Indus valley civilizations, much as in Mesopotamia. The vajralepa bitumen was made of wood-tar and was used to waterproof walls and structures in bath houses (Sengupta, 1971; Kumar, 1984; Carran et al., 2012). There is evidence of the early use of lime plaster in the ovens and pits of the houses in Kalibangan, Rajasthan, dated to the proto- Harappan period (3500–2500 BC; Sharma and Sharma, 2003), although it came into more common use since the last centuries of the 1st millennium BC. The pure lime binder was often obtained from ‘kankar’ (lime nodules) found abundantly among river gravel. Kankar contains ~70% calcite, 30% clay and a fraction of sand with other impurities, so that appropriate calcination of kankar may confer some hydraulic property to the mortar. Impure mortars with a variable sand/lime ratio are found in Buddhist settlements (Nagarjuna-Konda, 225–325 AD) and in the city of Kausambi, Uttar Pradesh (35–350 AD; Ghosh, 1989). A number of more recent buildings offer evidence of the widespread use of fired bricks and mortars, especially in mosques, temples (Thirumalini et al., 2015), monuments (Singh et al., 2014) and tombs (Gulzar et al., 2013). The Great Stupa at Sanchi, Madhya Pradesh (Fig. 11) is the oldest stone building in India (3rd century BC) and one of the largest fired-brick domes in the world.

Figure 11.

The Great Stupa at Sanchi (3rd century BC) is the oldest stone building in India and one of the largest fired-brick domes (photo by Nagarjun Kandukuru, CC-BY-SA-2.0).

Figure 11.

The Great Stupa at Sanchi (3rd century BC) is the oldest stone building in India and one of the largest fired-brick domes (photo by Nagarjun Kandukuru, CC-BY-SA-2.0).

The Charminar in Hyderabad (1591–1593 AD) was built with granite stones and mortar (Singh, 1993). Lime plasters were also used extensively for decorations on temples and other monuments. The investigation of the decorations applied on rock at the carved Ellora caves (6–11 century AD; Fig. 12) surprisingly showed that many of the plasters contained a substantial amount of kemp hurd (Cannabis sativa), so that the decorations provide one of the first examples of kemp-reinforced plaster (Singh et al., 2015). Furthermore, India offers a long tradition of organics mixed with lime allegedly to increase carbonation and durability: curd, jaggery, bel pulp (the fruit Aegel marmelos), lentils, black gram and oil of margosa (Chandra and Aavik, 1983; Singh et al., 1990).

Figure 12.

The Ellora caves show a spectacular labyrinth of rock carvings and paintings. Much of the artwork is plastered with one of the earliest examples of kemp-loaded lime of the 6th century AD.

Figure 12.

The Ellora caves show a spectacular labyrinth of rock carvings and paintings. Much of the artwork is plastered with one of the earliest examples of kemp-loaded lime of the 6th century AD.

The change in the paste properties resulting from the addition of organic compounds has long been known, (as mentioned briefly above) e.g. for traditional recipes for lime plasters in ancient Mesoamerica, China and India. Egyptians, Minoans and Romans modified the lime mortars with Arabic gum, animal glue, fig’s milk, egg yolk and many other organic substances in an attempt to improve the mechanical or working properties (Sickels, 1981). In the De Architectura Vitruvius described explicitly the mixing of lime with oil (calx ex oleo subacta) to improve waterproofing. The practice was passed down to the Middle Ages and Renaissance, especially in the case of quality mortars for decoration and in applications exposed to weathering agents. A large variety of organic and proteic substances was apparently tested, with mixed results: cereal dough, animal blood, fermented wine, beer, milk derivatives including cheese, bee’s wax, lard and many others.

3.2. Hydraulic mortars and pozzolans: the success of the ‘Vitruvian’ recipes

Mixing of lime plaster with partially or totally reacting aggregate marks the development from lime-based aerial mortar to hydraulic mortars. If the quartz aggregate of the mortar (formally inert) is replaced in part or fully with reactive Si, Al-rich material (generally defined ‘pozzolanic material’) then the highly alkaline environment created in the lime-saturated water induces the dissolution of the silicate or aluminosilicate phases and the subsequent precipitation of insoluble Si-rich hydrous phases (Hobbs and Siddall, 2011; Fig. 13).

Figure 13.

Reaction rim formed around a volcanic fragment in a lime matrix. The rim provides direct evidence of the pozzolanic reaction between the lime binder and the Si, Al-rich glass fragments inserted in the mix.

Figure 13.

Reaction rim formed around a volcanic fragment in a lime matrix. The rim provides direct evidence of the pozzolanic reaction between the lime binder and the Si, Al-rich glass fragments inserted in the mix.

The reactive pozzolanic material may be natural or synthetic silica glass, volcanic ash, radiolarite or diatomaceous earth, phytoliths, ceramics, clay, metallurgical slags, or any other reactive aluminosilicate compound. The materials employed in the past as pozzolanic additions in hydraulic lime mortars are also used today as supplementary cementitious materials (SCM) in the formulation of modern binders (Lothenbach et al., 2011; Snellings et al., 2012). Such materials can be represented in the lime–silica–alumina (CaO–SiO2–Al2O3) ternary diagram (Fig. 14). The reaction of lime with aluminosilicate phases is referred to as a ‘pozzolanic reaction’ or a ‘hydraulic reaction’. When the presence of reactive aluminosilicate phases stimulates the pozzolanic reaction in the binder, then it is called a ‘hydraulic’ or ‘pozzolanic’ binder (‘plaster’, ‘mortar’) (Massazza, 1998). If natural volcanoclastic materials were not available, hydraulicity in the binder was often obtained by the use of crushed ceramics (pottery, bricks, tiles) together with traditional inert aggregates (Siddall, 2011). Fired ceramic is actually compositionally similar to volcanic materials, so the pozzolanic character of thermally activated clays and fired clay-based materials has been investigated thoroughly (Baronio and Binda, 1997; Böke et al., 2006; Bakolas et al., 2008; Zendri et al., 2004; Fernandez et al., 2011). The best ceramic-material yielding pozzolanic reaction is the very fine-grained kaolinite-rich pottery in which metakaolinite-type phases were formed by firing in the temperature range 600–900°C (Bellotto et al., 1995). The use of clay minerals in the production of the ceramics as well as firing at higher temperatures induces the formation of less reactive phases, such as mullite (Gualtieri et al., 1995, Gualtieri and Bellotto, 1998), and thus reduced pozzolanic reactivity.

Figure 14.

Simplified lime-silica-alumina diagram showing the clinker phases and some of the phases formed during cement hydration and pozzolanic reactions. Modified from Lothenbach et al. (2011).

Figure 14.

Simplified lime-silica-alumina diagram showing the clinker phases and some of the phases formed during cement hydration and pozzolanic reactions. Modified from Lothenbach et al. (2011).

One of the earliest instances of pyrotechnologically produced lime mortar mixed with volcanic ash occurs at Aşıklı Höyük, Turkey (Hauptmann and Yalcin, 2001). The pozzolanic reaction observed in the Pre-Pottery Neolithic B (PPNB) Aşikli Hoyiik plaster (8th millennium BC), however, is probably accidental and there is no evidence of systematic use of hydraulic materials in this early period. The possibility indeed exists that the silica phytoliths and other siliceous minerals derived from plant ashes could indeed have induced pozzolanic-type reactions in other cases of primitive plaster technology.

As discussed above, hydraulic binders based on pozzolanic reactions developed in the Greek and Aegean world in the 2nd millennium BC (Maravelaki-Kalaitzaki et al., 2003; Moropoulou et al., 2005; Theodoridou et al., 2013). They became the technological basis for the highly successful binders used in later Roman architecture (Siddall, 2000). Between the Aegean tradition and the standardized adoption of the hydraulic mortar technology by Romans some thousand years later there is a fuzzy period of use and diffusion of these materials, possibly linked to cultural diffusion from the Eastern Mediterranean along the African coasts during the first Iron Age. Important clues to these pre-Roman developments are the hydraulic plasters of Tell es-Safi/Gath, Israel (Regev et al., 2010a) and the carbon-containing mortars (ash mortars) used in Punic cisterns of Tunisia (Lancaster, 2012). It is again important to note that the hydraulic mortars in all these examples are limited to flooring and cistern plastering, mainly with a waterproofing function. Consistently, the analysis of the excavated structures and the mortars from a residential quarter in the Punic-Roman area of Palermo, dated firmly to before the final conquest of the city by the Romans during the First Punic War (254 BC), show only wall and floor plasters, with crushed pottery present in two of the samples investigated (Montana et al., 2016).

The crucial evolution in the architectural use of hydraulic mortars occurred in a relatively short period in the first half of the 2nd century BC: the mortar is finally employed to strengthen masonry structures in both public and military buildings. It is the first fully recorded structural use of binders in architecture, in which the binder intimately links the units of the masonry and actively contributes to the mechanical strength of the composite structure. Marcus Porcius Cato (De agri cultura liber, dated approximately to 160 BC following the Oxford Classical Dictionary) described the systematic use of lime-based mortars as a binder in foundations, walls and complex architectural components of buildings (Greco, 2011). Following the critical chronological revision by Mogetta (2015), with which the present authors largely agree, the oldest known remaining example of concrete (caementa) in Rome is the Porticus Metelli, dated to ~130 BC. Most of the other concrete building traditionally dated to the late 3rd century or the early 2nd century BC (see table 2 in Mogetta, 2015) should be postdated to the last two decades of the 2nd century BC. Furthermore, there are recent indications that pozzolanic mortars were used to pour the foundations of fortification walls in wet areas far from Rome at very early periods (Aquileia: Bonetto et al., 2016; Ravenna: Costa et al., 2000). Apparently, Roman military engineers already knew that volcanic pozzolan performs better than crushed pottery in marshy or salt-water environments. If confirmed, such occurrences of pozzolanic reactions are even older than the examples in Rome, suggesting an early and rapid diffusion of the technology involving hydraulic reactions based on volcanoclastic material.

Table 2.

Main phase components of ordinary Portland clinkers.

Common phase nameMineral nameCompositionCement notationAppx. wt %
Alite (tricalcium silicate)hatruriteCa3SiO5C3S50–70
Belite (dicalcium silicate)larniteCa2SiO4C2S15–30
Aluminate (tricalcium aluminate)Ca3Al2O6C3A5–10
Ferrite (tetracalcium aluminoferrite)brownmilleriteCa2(Al, Fe)2O5C4AF5–15
Common phase nameMineral nameCompositionCement notationAppx. wt %
Alite (tricalcium silicate)hatruriteCa3SiO5C3S50–70
Belite (dicalcium silicate)larniteCa2SiO4C2S15–30
Aluminate (tricalcium aluminate)Ca3Al2O6C3A5–10
Ferrite (tetracalcium aluminoferrite)brownmilleriteCa2(Al, Fe)2O5C4AF5–15

Three major innovations and/or technological optimization in the use of the binders were introduced rapidly and systematically at the beginning of the 2nd century BC or shortly thereafter (Lechtmann and Hobbs, 1987; Siddall, 2000; Adam, 2005; Hobbs and Siddall, 2011; Brandon et al., 2014):

  • (1) The use of mortars to strengthen important architectural structures: for the first time binders are not limited to plastering and waterproofing.

  • (2) The systematic use of crushed ceramics (pottery, bricks, tiles) in terrestrial structures that required resistance to water. This technology, certainly derived from the Greek world, was carefully optimized in the so called opus signinum, widely used in cisterns, aqueducts, fountains and baths (Siddall, 2011).

  • (3) The exclusive use of highly pozzolanic volcanoclastic material in hydraulic mortars used to build structures in contact with sea water (Brandon et al., 2014).

Not surprisingly, it was in late Republican times (2nd–1st centuries BC) that the architectural capabilities of Roman engineers, previously limited by the robust but cumbersome properties of ashlar (the Servian walls of the 6th century BC were still built in opus quadratum), started to produce efficient, solid and durable buildings rapidly complying with the formula later encoded by Marcus Vitruvius Pollio: “Haec autem ita fieri debent, ut habeatur ratio firmitatis, utilitatis, venustatis” (De Architectura, 1.3.2; 29–23 BC). As the only architectural book surviving from classical antiquity, the Vitruvian statements and prescriptions are considered the primary source of information concerning Roman and Greek building techniques. Vitruvius’ De Architectura met with immense favour and reputation from the Renaissance to the end of the 19th century, becoming the conceptual reference for most Western architecture of the period. In his work, Vitruvius not only illustrated building techniques and architectural theories, but described at great length the nature and preparation of the materials, including mortars. As an example, Vitruvius in his Book II indicates clearly that the proportion of lime and sand must be increased if poor quality or marine sand is used as aggregate. His descriptions find neat experimental evidence in a number of recent investigations of Roman materials (Oleson et al., 2006; Gotti et al., 2008; Secco et al., 2018), where Vitruvius’ recipes for binder formulation and preparation found precise confirmation.

During the last part of Republican times, Roman engineers crucially improved the Aegean-derived technology of hydraulic binders by using slaked lime in a mixture with local high-alkali volcanic ash, first drawn from the banks of the river Tevere, and then from the volcanic sands found near Naples, at Pozzuoli; hence the name pozzolan, still in use today. Recent studies of the evolution of Roman mortars from Republican through Imperial times reveal specific changes in the composition and use of the mortar components. The mineral components of the ash outcrops within and around ancient Rome (especially the Pozzolane Rosse ignimbrite: Jackson et al., 2007; Marra et al., 2016) show that specific zeolite-rich tuffs with highly reactive properties were carefully selected from the very beginning in order to produce exceptionally hard and durable mortars. These important studies not only confirm the early chronology of Roman mortars identified by macroscopic observations (Mogetta, 2015), but also confirm the incredibly detailed description of the materials that Vitruvius indicated as ideal for the preparation of quality mortars (black and red sands, or harenae fossiciae: De Architectura 2.4.1). Further, Vitruvius states that this pozzolanic material is the only one that is able to harden under water (De Architectura 2.6, hence the name ‘hydraulic mortar’). The physicochemical and engineering characteristics of mortars used for the construction of Roman harbours have been investigated extensively in the frame of the ROMACONS project (Brandon et al., 2005, 2014; Oleson et al., 2006). Not only are the outstanding properties and durability confirmed, but the tuffs used in the mortars of the harbour of King Herod in Caesarea seem to have been transported all the way from the Bay of Naples. The Roman harbour builders knew very well that proper hardening of mortar at sea required good quality pozzolans, even at the cost of longdistance transportation.

The local occurrence of reactive volcanic sand (such as in Central Italy, or in the German Eifel area, known as Trass; Siddall, 2000), and the availability of recycled crushed pottery and bricks gave Roman engineers the appropriate technology to build flexible, innovative and durable architecture and ultimately set the basis for the efficient infrastructure of the Roman empire. In fact the Romans also developed the concept of lightweight robust structures by the use of innovative building techniques, such as the vaulting tubes, the use of appropriately shaped bricks, and the incorporation of lightweight pumiceous aggregates in the binder (Lancaster, 2005, 2015; Lancaster et al., 2010, 2011. The arches of the Colosseum and the Pantheon dome are reported to have been made with such innovative materials and techniques (Lancaster, 2011).

Note that the word cement (opus caementicium) in ancient Roman times referred to the concrete masonry of monuments composed of cm-sized brick and tuff fragments (caementa) used as aggregates and which are bonded by hydraulic mortars with alkali-rich, calcium-alumino-silicate volcanic ash sands (Lechtman and Hobbs, 1987; Lamprecht, 1996). Only in recent times has the meaning changed to refer to modern clinker-based materials.

The ability of producing and using excellent mortars was lost slowly after the fall of the Roman Empire. The dome of the Hagia Sophia Basilica in Costantinople (532–537 AD) is probably the last great Roman building formed by the monolithic pouring of Roman pozzolanic mortar based on crushed ceramics (Livingston, 1970; Moropoulou et al., 2002; Miriello et al., 2017). Lime-based mortars continued to be used through the Middle Ages, though in many cases the mortars were of rather low quality, made of partially burned lime, sometimes mixed with charcoal and clays, and the lime putty was frequently unaged and poorly slaked. The careless preparation made them mostly porous and degradable (Furlan and Bissegger, 1975; Franzini et al., 1999). Many of the Saxon, Norman and Longobardic materials are of this kind. The standardized production during the Roman Empire was thus followed by very local productions, mostly having only a small technological content, and it was only in specific and prestigious construction sites that high-quality binders were produced, as in the case of the Byzantine mosaics in Ravenna, or the Leaning Tower of Pisa (Franzini et al., 2000).

In the latter case, the absence of volcanoclastic material and the presence of CSH products hints at the possible use of very reactive silica sources, such as diatomaceous earths. Most of the mortars used through the Middle Ages until the Renaissance to build cathedrals, fortresses and palaces are lime-based (Alvarez et al., 2000; Franzini et al., 2000; Pecchioni et al., 2006). However, some binders show a limited hydraulicity (Moropoulou et al., 2000; Elsen et al., 2004) due to pozzolanic reactions. Although discontinuous, the tradition of making hydraulic mortars by the use of crushed ceramics persisted in several regions of the Roman Empire and beyond: it is called cocciopesto in Renaissance Italy, horasan in Turkey, homra in the Middle East, surkhi in India.

A peculiar kind of traditional material produced by clay activation is called sarooj. It was apparently used widely in ancient Persia and other areas around the Persian gulf, especially for cisterns and waterproof structures (Al-Rawas et al., 1998, 2001). It is claimed that a number of ancient temples and buildings, such as the Elamite zigurrat at Chogha Zanbil, Iran (Fig. 7) were built partially using sarooj, although experimental evidence is scarce. The reported preparation of the material indicates that a mix of clays, dung and water was sun-dried into decimetre-sized blocks, which were then fire-heated for activation. The final product was ground and mixed with lime to produce the final binder (Masoumi et al., 2015). Sarooj seems to be the earliest example in which thermal activation of clay was consciously and systematically employed to obtain hydraulic reactions.

As will be discussed below, the technology based on thermally activated clays is regarded as one of the future solutions for the replacement of modern Portland-based clinker with more sustainable products (Scrivener and Favier, 2015). As a matter of fact, our understanding of the pozzolanic reactions that occurred in ancient hydraulic binders allows modern interpretation of their mechanical durability (Moropoulou et al., 2000; Charola et al., 2005), and has fundamental implications for the development and technological control of modern cement alternatives to Portland clinkers (Mahasenan et al., 2003; Schneider et al., 2011). On a technical note, the protocols of separation and characterization of the binder fractions for reliable radiocarbon dating of ancient mortars require adequate understanding of the phases present and their reaction history (Lindroos et al., 2011; Addis et al., 2016).

The presence and extent of pozzolanic reactions in ancient mortars is commonly assessed by:

  • (1) measurement of the mechanical resistance to compression tests, which is substantially greater than those measured on traditional lime mortars,

  • (2) calculation of empirical parameters derived from bulk-chemistry measurements (i.e. hydraulicity index, cementation index),

  • (3) characterizing the nature and micro-textural features of the mineralogical phases present in the binder fraction of the composite, which are the result of pozzolanic reactions.

Testing the mechanical resistance is an indirect bulk measurement and leaves space for ambiguities in the interpretation of the mechanisms that lead to the development of the physical properties. The ‘hydraulicity index’ (HI = SiO2 + Al2О3/СаО) or the ‘cementation index’ (CI = 2.8 SiO2 +1.1 A12O3 + 0.7 Fe2O3/CaO +1.4 MgO) are generally proportional to the amount of Si, Al-rich species in the mortar (Elsen et al., 2012), though the presence of aluminosilicate phases is not sufficient to indicate that the pozzolanic reaction did actually take place to a sufficient extent in the binder, as they can be inert or very slowly reacting.

On the other hand, a thorough mineralogical characterization of the phases and of the textures resulting from the lime-pozzolan interaction yields direct evidence of the pozzolanic reaction. Adequate characterization, therefore, requires identification of reaction products (by X-ray powder diffraction (XRPD), FTIR, Raman spectroscopy, or other micro-analytical techniques) and/or micro-imaging of the reaction textures, such as the reaction rims formed around the pozzolanic particles through dissolution-recrystallization processes (Fig. 13; see for example: Maravelaki-Kalaitzaki et al., 2003; Diekamp et al., 2012). The limiting factor of the pozzolanic reaction rate in general is the dissolution kinetics of silicate phases. The issue is fundamental when assessing the reactivity ofmaterials to be used as supplementary cementitious materials (SCM) in modern binder formulations (Malhotra and Mehta, 1996; Lothenbach et al., 2011; Snellings et al., 2012).

The hydrous phases formed by the pozzolanic reaction have a variable composition depending on the chemistry of the system (Fig. 14). They range from pure C-S-H phases in the lime-silica join (tobermoritic Ca, Si-hydrates; Richardson, 1999, 2004) to more complicated C-A-S-H phases as the Al activity increases (Hong and Glasser, 2002, L’Hôpital et al., 2015, 2016). Zeolite-like phases are favoured in complex N-K-C-A-S-H environments, and their formation is reported to be enhanced by interaction with sea water (Jackson et al., 2012, 2013, 2017). It is the interaction between sea water and the volcanic tuff that yielded tobermorite and zeolitic phases and produced the extremely hard and durable binders of Roman harbours.

3.3. Natural hydraulic lime (NHL) mortars

A particular type of hydraulic binder was developed in Europe in the 18th and 19th centuries by firing impure limestones containing clays in lime kilns; they are called natural hydraulic limes (NHL) or “Roman cements” (Weber et al., 2012). In these natural hydraulic binders the reactive phases are not added as aggregate, but formed in the kiln through the reaction of the clays and the quicklime. They can be considered the precursors of modern Portland clinker. NHL were very popular for building construction and façade decoration in Central Europe in the 19th century (Callebaut et al., 2000, 2001). They were, and are still, used extensively for restoration of historical buildings (Maravelaki-Kalaitzaki et al., 2005; Gosselin et al., 2009; Bras and Henriques, 2012) because of their good mechanical properties and compatibility with ancient materials.

A very early instance of production and use of NHL in the 14th century AD was identified during the investigation of the mortars and slags of the Gothic Obřany Castle, Moravia (Kropáč and Dolníček, 2013): the interpretation is that the lime binder incorporated high-temperature phases derived from the kiln lining and local metallurgical activities. Slags from ore processing were also observed in the mortars of the medieval archaeological complex at Montieri, Tuscany, Italy (Chiarelli et al., 2015), which is located in an area of intense exploitation of argentiferous ores.

Both pozzolan-added mortars and NHL were used in the Czech Republic to build 14th century bridges, such as Charles Bridge in Prague and the Gothic bridge in Roudnice (Frankeová et al., 2012). The slightly hydraulic character of the Narni bridge, in Central Italy (3rd century AD) is thought to be derived from the accidental firing of impure limestones, containing cherts (Cantisani et al., 2002; Frankeová et al., 2012). In extreme cases, the burning in lime kilns of chert-containing limestones in the presence of alkali lowering the melting point of silica yields the production of amazingly coloured silica glasses, which were found at the base of the furnace after firing (Artioli et al., 2009).

Vitruvius recommended the use of very white and pure limestone for the production of lime in classical times. It appears that whenever the Vitruvian recipes were abandoned or not followed closely, the accidental use of impure limestones with various amounts of silica or aluminosilicate phases randomly produced binders with very variable degrees of hydraulicity. Sometimes the fine-grained size of the original material and the heterogeneity of the microtexture makes it very difficult to assess the degree of hydraulicity and/or deduce unambiguously the complex dynamic of the production process (Riccardi et al., 2007).

The emerging picture is one of unstandardized binders and largely uncontrolled production processes from late antiquity until approximately the 18th century AD, when systematic experiments were carried out to produce optimized materials.

4. The development of modern cement materials and the hydration process

A significant change from traditional lime mortars was made by John Smeaton in England in 1756, when he was involved in the reconstruction of the Eddystone lighthouse (Blezard, 2003). As the story goes, he was driven by the need to develop a masonry construction durable in a marine environment and thus built using a binding lime mortar that did not dissolve in seawater. Among several attempts, he also departed from the Vitruvian recommendations of using pure white limestone. Using clay-rich carbonates of marly composition he obtained better hydraulic properties than lime. As discussed above, this class of materials may be defined as natural hydraulic limes and can be considered intermediate between slaked lime and modern Portland cement. Eventually the material that Smeaton selected for the lighthouse was a mortar prepared with equal proportions of local argillaceous limestones (blue Liassic limestones) and pozzolan from Civitavecchia, Italy, the closest stuff he could access resembling the ancient Roman material. Slightly improved mixtures of this kind were in use until the introduction of Portland cement.

In the first half of the 19th century the search for optimal hydraulic binders was pursued actively in several countries (Bentur, 2002; Blezard, 2003). In England Smeaton was testing alternative formulations of hydraulic mortars, and J. Parker introduced and patented a so-called “Roman cement” (Patent by James Parker, of Northfleet, Kent, England, No. 2120, 1796), defined as a “cement or tarras to be used in aquatic and other buildings and stucco work”. It was made by calcination of nodules of argillaceous limestone (known as septariae) and it produced a quick-setting cement. In France, Louis Vicat’s experiments (Vicat, 1818) led to the preparation of hydraulic lime by calcination of a mixture of high-grade quicklime (produced by the chalk of the Upper Cretaceous carbonatic formation of the Paris Basin) and clay (Vicat, 1828). His formulation, called the “twice-kilned” process, met with considerable success and led his son Joseph Vicat to establish the well known Vicat Cement company. This is considered by many to be the predecessor of Portland cement.

A lot of patents were issued around the same time establishing plants in southern England, including the London area. The most famous one is that related to the three-stage process of Joseph Aspdin (patented in 1824), who named his product ‘Portland cement’, because, at that time, the Portland limestone had a reputation among builders for quality and durability, and he wanted to capture the similitude between his cement and Britain’s favoured quarried stone. Portland cement was marketed as an improvement in the production of artificial stone. In one of the several plants established by Aspdin or his son, the temperatures were running high enough to produce partial or complete vitrification and crystallize alite, as shown by the retrospective analysis of the type of clinker material from Aspdin’s kiln (Blezard, 2003). The ‘clinker’ is the reactive product formed by cooling from the high-temperature processing (1450°C) of the limestone and clay mixture within the kiln. The temperature is such that partial fusion occurs and the reacted molten material forms nodules that are partly crystalline and partly vitrified, the whole material being highly reactive with water. The four major phases making up the clinker are reported in Table 2, though the real situation is made more complicated by the existence of several polymorphs for each phase, and by compositional deviation from stoichiometry (Taylor, 1997). The basic chemical composition of Portland cement is shown in Fig. 14, where it is evident that the composition of the two major phases (alite and belite) lies on the CaO–SiO2 join as a result of the lime–silica reaction. The hydration products, composed mainly of calcium silica hydrates (C-S-H) and portlandite also lie in the same portion of the diagram.

Following Blezard (2003), the historical evolution of clinkers after the illustrated pioneering experiments moved from proto-Portland materials (i.e. Aspdin’s original patent), which shows limited interaction between CaO and SiO2 because of the limited temperature in the kiln, to meso-Portland materials, which are very heterogeneous materials showing some silica–lime interaction and containing mostly belite and some alite, and finally to normal-Portland cements as we know them today. The main characteristics of modern Portland clinkers are derived mostly from the use of rotary kilns in place of the traditional shaft kilns, a technical development that also allows continuous production in place of the batch process. The carefully-controlled initial formulation of calcareous and argillaceous components, together with the use of the rotary kiln that determines a long permanence at high temperature and continuous mixing, helps to: (1) minimize the amount of unreacted lime; (2) maximize the alite/belite ratio; and (3) obtain the appropriate crystal size of the mineral components, commonly in the range 10–40 μm. Modern clinkers contain about 60–65 wt.% of C3S, and <2 wt.% of unreacted free lime. The standard reaction properties of modern Portland clinker are essentially due to a high alite/belite ratio and to a careful control of the grinding of the clinker into a fine powder.

The very reactive Portland cement powder is mixed with water to produce a final hardened material through a series of complex reactions, the so-called ‘hydration process’, involving dissolution of the crystal phases, surface reactions, gel formation, precipitation of new phases and textural changes (Taylor, 1997; Gartner et al., 2002; Bullard et al., 2011). The different crystal phases present in the clinker have very different reactivities, C3A having the highest and C2S the lowest. In fact C3A is so reactive exothermally in water that it can cause unwanted rapid setting of the paste (flash set), with consequent loss of workability. Therefore calcium sulfate (commonly gypsum) is usually added to the clinker in the amount of ~4–8 wt.% as a set-controlling agent, because the sulfate ion retards the dissolution of the clinker phases, and promotes the formation of ettringite. The finely powdered mixture of clinker and gypsum is marketed as standard Portland cement (also called OPC = ordinary Portland cement), which is then mixed with water in the ratio water/cement >0.38, i.e. the least amount of water necessary for complete hydration of the cement phases. As in ancient binders (Table 1), when an aggregate material is added to the paste we have mortar (fine aggregate, such as sand with grain size <1 mm) or concrete (fine and coarse aggregate, such as coarse sands or gravel). They can both be considered to be cement composites, with the aggregate having the role of reducing the formation of fractures during the shrinkage that accompanies the hydration and hardening; for the same reason temper is added to pottery clays before firing. The aggregate may be composed of any type of loose or ground rock, and it is assumed not to react with the cement paste (hence it is referred to inappropriately as the ‘inert’ component), though this is not necessarily the case.

Upon mixing with water, the clinker phases react at different times to produce first a series of intermediate phases (the so-called AFt and AFm phases) such as ettringite (Ca6Al2(SO4)3(OH)1226H2O) or monosulfoaluminate (Ca4Al2(SO4)O612H2O), and then the reaction proceeds to the final hydrous phases: portlandite and amorphous calcium silicate hydrate (C–S–H), which are the phases forming the interlocked gridwork of the material and producing high mechanical resistance. Figure 15 shows environmental scanning electron microscope (ESEM) evidence of the growth of ettringite and C–S–H at different times on the surface of the clinker grains. It is important to understand that it is the microstructure of the material, that is the final assemblage of crystalline and amorphous phases that governs the macroscopic and engineering properties of the material (Thomas et al., 2011; Scrivener et al., 2016). With time, portlandite will eventually convert into calcite through a carbonation reaction with atmospheric carbon dioxide, so that abundant calcite is found in old cements.

Figure 15.

(a) Prismatic crystals of ettringite growing amidst C-S-H felt during the hydration of a Portland cement, and (b) well developed platy crystals of Portlandite. Images obtained by ESEM. (Courtesy of D. Salvioni, Mapei S.p.a.).

Figure 15.

(a) Prismatic crystals of ettringite growing amidst C-S-H felt during the hydration of a Portland cement, and (b) well developed platy crystals of Portlandite. Images obtained by ESEM. (Courtesy of D. Salvioni, Mapei S.p.a.).

Reaction kinetics play a crucial role in determining the final microstructural properties. The completion of the hydration process may take days, months, or even years, depending on crystal size, defectivity and polymorphism of the phases, porosity of the paste, environmental conditions, etc. The system is so complex that reactions can be inhibited for a long time. It is often observed in old concrete that highly reactive species such as aluminates are still present years or decades after manufacturing (Secco et al., 2014). Many of the practical problems in the modern cement industry derive from the lack of control of clinker composition, poor concrete design, or sloppy practice: even small changes may affect the hydration kinetics and determine substantial degradation of the engineering properties. Incidentally, the same problems, mostly due to human factors such as incompetence and fraud, were present and well recorded in Roman times (Oleson, 2011).

Strength development is related to the degree of hydration and to the speed of the process. In general, the slower the hydration kinetics, the higher the compressive strength developed. This is one of the differences observed between modern clinkers and those produced in the early part of the last century. Modern cement is required to develop high resistance to compression (>40 MPa) within a few days of emplacement, whereas early 1900s cements developed high strengths (in the range of 20–30 MPa) over much longer periods, because of the greater belite content. This has some consequences also in terms of durability. High-compression resistance combined with tensional resistance are, of course, obtained by steel reinforced concrete (SRC), which is a composite in which the concrete is poured and solidified around a metal skeleton. The French-Swiss architect, Le Corbusier, was one of the first to understand and exploit the properties of SRC in modern architecture. He had discovered the use of reinforced concrete very early in Paris from one of the pioneers of its use, architect Auguste Perret, and then employed it to realize his architectural vision (Fig. 16). He later wrote: “Reinforced concrete provided me with incredible resources, and variety, and a passionate plasticity in which by themselves my structures will be rhythm of a palace, and a Pompeiian tranquility” (Letter to Auguste Perret, 1915).

Figure 16.

Reinforced concrete structures by Charles-Édouard Jeanneret (Le Corbusier): (a) The convent of Sainte Marie de La Tourette, France (1953–1960) (photo by Alexandre Norman, French Wikipedia, CC-BY-SA-3.0); (b) The palace of Assembly, Chandigarh, India (1952–1961) (photo by English Wikipedia, CC-BY-SA-2.0).

Figure 16.

Reinforced concrete structures by Charles-Édouard Jeanneret (Le Corbusier): (a) The convent of Sainte Marie de La Tourette, France (1953–1960) (photo by Alexandre Norman, French Wikipedia, CC-BY-SA-3.0); (b) The palace of Assembly, Chandigarh, India (1952–1961) (photo by English Wikipedia, CC-BY-SA-2.0).

Nowadays only ~35% of the cements produced industrially for the global market are OPC, and most of the materials are special composite formulations (Odler, 2000; Chatterjee, 2002), where special components or SCM are added to enhance specific physicochemical or mechanical properties, such as resistance to alkali or sulfates, thermal resistance, or low-heat emission. The main added constituents are: (1) latent hydraulic components (granulated blast furnace slags, class C fly ash) that have selfcementing properties that need to be activated by OPC; (2) pozzolanic aluminosilicate components (class F fly ash, silica fume, metakaolin, pozzolan) that have no selfcementing properties and need to be activated by portlandite; and (3) non-reactive or poorly reactive components that modify the grindability of the clinker or the rheology of the paste.

Because of the low market cost of cement, the materials added to the clinker are large-volume but low-cost byproducts of other industrial activities. Therefore on one hand the production of cement represents a virtuous route to recycle large quantities of waste material (e.g. slags from the metallurgical industry, fly ash from coal plants); on the other hand the market for special cements will need alternative materials should the global changes in metal and energy production decrease the availability of SCM materials in the future.

One of the most important properties of modern cement pastes and concrete composites is fluidity: it ensures the possibility of transportation, pumping, levelling concrete to fit modern architectural requirements, and also proper consolidation by grouting. The rheological and working properties of the cement and concrete are so important that they are now controlled invariably by the use of chemical admixtures (water-soluble organic polymers) that allow good fluidity of the paste with a smaller water/cement ratio. The net result is also a lower porosity of the paste and a greater mechanical strength: ultra-high performance concrete and high-strength concrete are made this way, they can reach compression strengths in excess of 150 MPa. The modern generations of plasticizers, ensuring fluidity at low water content are called water-reducing admixtures (Chandra, 2002; Edmeades and Hewlett, 2003). Besides rheology, organic and inorganic additives are also used to control specific properties of the mortars and cements, such as air entrainment (for better resistance to freeze and thaw cycles), acceleration or retardation of the setting (to control the time of progressive increase in mechanical resistance; Cheung et al., 2011) and even resistance to chemical attack. Virtually all modern concrete formulations include polymeric admixtures to optimize performances.

How do we investigate cement materials? At the industrial level, most quality controls are done by optical microscopy, X-ray fluorescence (XRF) and XRPD, with the quantitative phase analysis by XRPD offering a number of crucial advantages over bulk chemical analysis by XRF. Cement producers are among the most active users of advanced on-line testing protocols and instrumentation using automatic XRPD, including full-profile refinement of all clinker phases (Bellotto and Signes-Frehel, 1998; Manias et al., 2000; De la Torre and Aranda, 2003; Bequette and Dhanjal, 2011; Snellings, 2016).

At the research level, the cement system is complex enough that one experimental technique alone is hardly sufficient to unveil the fine interplay between all chemical reactions acting simultaneously during hydration. Furthermore, the system is extremely sensitive to any environmental perturbation, especially dehydration, so that sample preparation without artefacts is a crucial part of any experiment. Virtually all experimental techniques have been employed to characterize and understand the behaviour and evolution of cement systems. In this chapter we will mention only some of the most recent developments providing a better insight into fundamental mechanisms of cement hydration processes. Time-resolved XRPD is one of the most powerful techniques for following the evolution of the cement/water system during hydration (Dalconi et al., 2008; Hesse et al., 2011; Valentini et al., 2015). It allows appropriate quantification of the phases and evaluation of reaction kinetics (Fig. 17). If reaction enthalpies are sufficiently well known (Matschei et al., 2007; Damidot et al., 2011), then it is possible to back-calculate the measured curves from isothermal calorimetry and discriminate the underlying reactions (Hesse et al., 2011; Jansen et al., 2012; Valentini, 2013).

Figure 17.

Time resolved XRPD patterns of a cement paste during the hydration process.

Figure 17.

Time resolved XRPD patterns of a cement paste during the hydration process.

The use of synchrotron radiation, of course, allows access to much faster reaction times with respect to laboratory instruments (Merlini et al., 2007, 2008; Snellings et al., 2010), down to the millisecond timescale (Schlegel et al., 2012). Synchrotrons offer the advantage of highly brilliant and coherent radiation, so that experimental techniques can be designed flexibly to suit complex samples (Aranda, 2016). Simultaneous and combined investigations are thus possible only at large scale-facilities. Concerning cements, ultra-high resolution imaging (Harutyunyan et al., 2009; Monteiro et al., 2011) and sub-micron computed tomography (Artioli et al., 2010; Parisatto et al., 2015) provide considerable advances in understanding the 3D evolution of the microstructure of the material in a totally non-invasive mode (Fig. 18). Furthermore, the innovative combination afforded by diffraction-enhanced tomographic imaging proved to be an extremely powerful tool for the investigation of complex materials (Voltolini et al., 2013), and allowed, for the first time, direct imaging of nucleation processes (Artioli et al., 2014a,b).

Figure 18.

Virtual modelling of the microstructural evolution of cement can be compared directly to the experimental results obtained by computed micro-tomography (μ-CT).

Figure 18.

Virtual modelling of the microstructural evolution of cement can be compared directly to the experimental results obtained by computed micro-tomography (μ-CT).

As a further link between the cement world and mineralogy, there is only one known natural occurrence of the calcium silicate phases (hatrurite, larnite) that are commonly produced in cement kilns. It is from a geological formation called the Hatrurim Formation, and it is exposed in various areas around the Dead Sea in Israel (Hatrurim Junction, near Arad), Palestine and Jordan (Maqarin). It is interpreted to occur as the result of pyrometamorphism of marls and limestones derived from gas or bitumen ignition in the underlying hydrocarbon-loaded formation (Burg et al., 1991; Gilat, 1998; Sokol et al., 2007). The natural combustion produced this unique rock formation of thermally metamorphosed ‘cement zones’ which are very close analogues of industrial cements. In the Hatrurim Formation the calcium silicate phases occur together with a number of exotic high-temperature mineral phases (shulamitite, bentorite, gazeevite, stracherite, zoharite, zuktamrurite, and others), most of them found only in this unique type locality.

The Maqarin site, located along the Yarmouk river near the Jordan–Syria border, has been investigated extensively because the subsequent interaction with groundwater caused the formation of hyperalkaline waters and C–S–H phases in the fractures of the HT-metamorphosed rocks. Such unique features were studied in detail in order to understand the long-term leaching and cation mobility in the only known natural analogue of a modern radioactive-waste repository. The investigation project was called The Maqarin Natural Analogue Project (Khoury et al., 1992; Alexander and Smellie, 1998; Alexander and Blaser, 2002). This is another example showing the interplay of knowledge between natural and synthetic systems. This knowledge encompasses mineralogy, geology, hydrology, crystal chemistry, geochemistry and a number of other disciplines, and it is fundamental when tackling problems at a large or global scale.

4.1. Binders of the future

Modern cement formulations based on Portland clinkers are coming under serious criticism because of environmental issues. Cement is one of the industrial materials embodying the least amount of energy per unit volume, if compared, for example, with polymers, metals, and technical ceramics (Fig. 19). However, at present, modern society requires huge amounts of cement for infrastructures: the world production in 2016 was estimated at 4.2 × 109 tons/year (www.statista.com/statistics/219343/cement-production-worldwide/), higher than oil and gas, and second only to water. This is considered a problem because of the large emission of CO2 during cement production (Worrell et al., 2001; Barcelo et al., 2014; Gartner and Hirao, 2015), estimated at ~1 ton of CO2 emitted per ton of OPC. The emission of CO2 derives from the fuel used in the kiln, grinding, transportation, but above all from the de-carbonation of limestone.

Figure 19.

Young’s Modulus vs. embodied energy per unit volume. (Chart created using CES EduPack, 2017, Granta Design Ltd. http://teachingresources.grantadesign.com/Charts-overview).

Figure 19.

Young’s Modulus vs. embodied energy per unit volume. (Chart created using CES EduPack, 2017, Granta Design Ltd. http://teachingresources.grantadesign.com/Charts-overview).

Increasing global concerns about sustainability and environmental compatibility (see the Intergovernmental Panel on Climate Change (IPCC) website: www.ipcc.ch/) stimulate active research towards more eco-friendly choices of materials (Ashby, 2013). The life-cycle assessment of building materials and methods is an active field of research, and concepts such as the ‘transcendent quality’ of building materials (Mora, 2007) and that of ‘life-cycle thinking’ (Buyle et al., 2013) are finally entering the lexicon of construction planning. Comparative assessments of the life and energy cycles of traditional and alternative cements and mortars are on their way (Weil et al., 2009; Chen et al., 2010; Jiang et al., 2014; Ouellet-Plamondon and Habert, 2015). Alkali-activated materials and fly-ash/slag-based geopolymers are being tested actively in the formulation of clinker-free binders (Shi et al., 2006; Provis and Van Deventer, 2009, 2014; Pacheco-Torgal et al., 2015). Thermally activated clays are also proposed to be a sustainable solution in the long time-span (Scrivener and Favier, 2015). It is accepted widely that the infrastructure and housing needs of modern society cannot avoid being dependent on cement-type materials (Schneider et al., 2011), because the ratio between engineering properties and cost is more advantageous than for any other available material. Present trends and efforts are therefore clearly directed towards sustainability of construction materials (Liew et al., 2017), which is the key word for future research and planning: despite the optimistic claims of the cement industry (Damtoft et al., 2008) cement is certainly one of the materials in need of substantial improvement (Shi et al., 2011; Flatt et al., 2012; Kurtis, 2015).

5. Conservation of binders in architecture – Binders for conservation

Conservation of historical buildings and ancient architecture is a very intricate task. Sometimes the technical problems of conservation of the materials are not even the major difficulty: most of the problems are commonly connected with the management and decision-making of what to preserve and why. Economic, social, cultural and organizational constraints ought to be resolved before technical plans are developed (Aygen, 2013; Forsyth, 2007a. Are we sure we can distinguish the fuzzy boundaries of preservation, conservation, restoration, reconstruction, consolidation or stabilization? Following the indications of the ICOMOS Venice Charter (1964, International Charter for the Conservation and Restoration of Monuments and Sites, www.icomos.org/charters/venice_e.pdf), preservation involves the minimal repair and maintenance of remains in their existing state, possibly avoiding further degradation. Restoration involves the removal of subsequent additions in order to return to the pristine state of the building. In such a case archaeological and scientific support (dating the materials for example) are fundamental in understanding the different construction phases. Reconstruction also involves returning a building to an earlier state, but involves introducing new/old materials to complete or stabilize the structures. Therefore compatibility and reversibility are at stake, and the fundamental concept of authenticity should be pondered carefully (ICOMOS Nara Charter on Authenticity, 1994, www.icomos.org/charters/nara-e.pdf). Conservation may involve one or more of the previous interventions, as well as the adaptation of buildings to new uses. Present emphasis of engineering interventions is towards building retrofitting, i.e. adding new technology to old structures in order to comply with modern legislation or lifestyle standards, especially concerning seismic aspects (safety), energetics (environment) and comfort. The attitude to building preservation has shifted constantly in the past, and we can be sure that conservation philosophy (Earl and Saint, 2015) in the future will be different from that of today.

Leaving to managers and planners the general problems, which are clearly beyond the purpose of this review, there are two important points that should be kept in mind. The first one concerns the sustainability of any architectural or structural intervention: this includes a reasonable balance between resources and objectives, and then adequate planning aimed at monitoring the success and durability of the intervention. Monitoring and continuous maintenance are often neglected, mainly because of sheer costs, and this frequently jeopardizes, in the long run, the results of many technical interventions, even if they were carried out with state-of-the-art protocols. The second point concerns the planning of conservation at very early stages of the intervention plan, i.e. as soon as the building/site is earmarked for attention or, as in the case of archaeological excavations, even before the excavation has started. Present trends contemplate parallel planning of archaeological works and conservation (Agnew and Bridgland, 2006; Sullivan and Mackay, 2013; Pedelì and Pulga, 2013).

No matter what the intervention is going to be, materials are important. Prior to any preservation or conservation action, a considerable effort to identify the materials originally used and to assess the constructive techniques employed should be made, along with a careful analysis of compatibility with new materials and a critical evaluation of stability and permanence of restoration works to be undertaken. In conservation repair work, it is therefore imperative that an understanding of the structure and the materials be gained before specifying and undertaking any work (Forsyth, 2008). For ancient lime-based architectures this is particularly important, because the state of the structure depends on the materials employed, the quality of the application, the environmental conditions, the continuous or discontinuous use (abandonment) of the structure, etc.

The conservation process should encompass: (1) extensive diagnostics at various scales, including the characterization of materials; (2) modelling and structure analysis; (3) selection and testing of materials and architectural components; and (4) the intervention plan. The last should comply as much as possible with the guidelines of the ICOMOS Venice charter and the Nara document on authenticity.

Each structure must be treated as a specific case, involving a particular combination of material properties, architectural character and environmental parameters. Reaching a compromise between the structural intervention and the integrity/authenticity of the original structure is the most challenging task.

The choice of mortars and plasters to be used in conservation is important in relation to the three major factors governing the performance of historic fabric: porosity, flexibility and strength. Any change in these parameters will affect seriously the stability and durability of the structure. Therefore, the nature and properties of the materials employed must be controlled carefully in terms of compatibility with the existing materials (Van Balen et al., 2005). If the intervention is extensive, reversibility is hardly possible. Extensive work has been done to characterize and optimize repair mortars and grouts (e.g.Maurenbrecher, 2004; Faria et al., 2008; Schueremans et al., 2011). Compatibility between mortars and repaired stone materials has been addressed specifically (Isebaert et al., 2014). While in the past Portland cement has been used variously to strengthen historical structures, it is now widely accepted that the use of OPC or formulations using OPC are detrimental to ancient structures in terms of mechanical and chemical incompatibility. OPC has two major adverse effects. The first is that the mechanical behaviour in terms of compressive strength or Young’s modulus is much greater than that of lime mortars, thus creating rigid insertions in the fabric and reducing flexibility. The second is that OPC contains sulfate ions that are inevitably leached into the structure and redeposited as salts, usually at the surface, causing well known effects of surface deterioration (detachments, spalling, efflorescence, etc.). Sulfate salts are also deleterious to bricks and stone units of masonry (Fig. 20). For these reasons OPC has been virtually banned from all interventions to pre-industrial age buildings and ancient lime-based architecture. From all evidence, historical lime and hydraulic mortars proved to be less performing but more durable than 20th century reinforced concrete. Actually, the restoration and preservation of last century historical buildings based on Portland concrete is turning to be a diffuse and urgent problem, particularly where it is exposed and subject to damage from reinforcement corrosion (Forsyth, 2007b; Macdonald, 2008).

Figure 20.

Brick masonry of an old factory converted to a modern building. The OPC cement used to repoint the joints is deleterious in terms of rigidity and salt leaching.

Figure 20.

Brick masonry of an old factory converted to a modern building. The OPC cement used to repoint the joints is deleterious in terms of rigidity and salt leaching.

Acknowledgments

Small parts of the text have been adapted from chapter 3.2 of Artioli (2010).

References

Abrams
,
E.M.
and
Freter
,
A.
(
1996
)
A Late Classic lime-plaster kiln from the Maya centre of Copan, Honduras
.
Antiquity
 ,
70
,
422
428
.
Adam
,
J.P.
(
2005
)
Roman Building: Materials and Techniques
 .
Routledge
,
London
.
Addis
,
A.
,
Secco
,
M.
,
Preto
,
N.
,
Marzaioli
,
F.
,
Passariello
,
I.
,
Brogiolo
,
G.P.
,
Chavarria Arnau
,
A.
,
Artioli
,
G.
and
Terrasi
,
F.
(
2016
)
New strategies for radiocarbon dating of mortars: Multi-step purification of the lime binder
. Pp.
665
672
in:
Proceedings of the 4th Historic Mortars Conference – HMC 2016
(
I.
Papayianni
M.
Stefanidou
and
V.
Pachta
, editors).
Aristotle University of Thessaloniki
,
Greece
.
Affonso
,
M.T.C.
and
Freiberg
,
E.P.
(
2001
)
Neolithic lime plasters and pozzolanic reactions. Are they occasional occurrences?
Pp.
9
13
in:
Lux Orientis. Archaeologie zwishen Asien and Europa
  (
R.M.
Boehmer
and
J.
Maran
, editors).
Festschrift fur Havald Hauptmann zum 65 Geburstag. Verlag Marie Leidorf GmbH.
Rahden/Westfalia, Germany.
Agnew
,
N.
and
Bridgland
,
J.
(editors) (
2006
)
Of the Past, for the Future: Integrating Archaeology and Conservation
 .
Proceedings of the Conservation Theme at the 5th World Archaeological Congress
,
Washington, DC
, 22–26 June 2003.
Getty Publications
,
Los Angeles, California, USA
.
Alexander
,
W.R.
and
Blaser
,
P.C.
(editors) (
2002
)
The use of technical natural analogues in radioactive waste disposal
 .
Nagra Unpublished Project Report,
Nagra, Wettingen, Switzerland
.
Alexander
,
W.R.
and
Smellie
,
J.A.T.
(
1998
)
Maqarin natural analogue project: synthesis report on Phases I, II and III
 .
Nagra Unpublished Project Report,
Nagra, Wettingen, Switzerland
.
Al-Rawas
,
A.A.
,
Hago
,
A.W.
,
Corcoran
,
T.C.
and
Al-Ghafri
,
K.M.
(
1998
)
Properties of Omani artificial pozzolana (sarooj)
.
Applied Clay Science
 ,
13
,
275
292
.
Al-Rawas
,
A.A.
,
Hago
,
A.W.
,
Al-Lawati
,
D.
and
Al-Battashi
,
A.
(
2001
)
The Omani artificial pozzolans (sarooj)
.
Cement, Concrete and Aggregates
 ,
23
,
19
26
.
Alvarez
,
J.I.
,
Navarro
,
I.
,
Martın
,
A.
and
Casado
,
P.G.
(
2000
)
A study of the ancient mortars in the north tower of Pamplona’s San Cernin church
.
Cement and Concrete Research
 ,
30
,
1413
1419
.
Ambers
,
J.
(
1987
)
Stable carbon isotope ratios and their relevance to the determination of accurate radiocarbon dates for lime mortars
.
Journal of Archaeological Science
 ,
14
,
569
576
.
Aranda
,
M.A.
(
2016
)
Recent studies of cements and concretes by synchrotron radiation crystallographic and cognate methods
.
Crystallography Reviews
 ,
22
,
150
196
.
Arandigoyen
,
M.
,
Bicer-Simsir
,
B.
,
Alvarez
,
J.I.
and
Lange
,
D.A.
(
2006
)
Variation of microstructure with carbonation in lime and blended pastes
.
Applied Surface Science
 .
252
,
7562
7571
.
Arkun
,
B.H.
(
2003
)
Neolithic plasters in the Near East: Çatalhöyük Building 5, a case study
. Master’s Thesis,
University of Pennsylvania
.
Artioli
,
G.
(
2010
)
Scientific Methods and Cultural Heritage: An Introduction to the Application of Materials Science to Archaeometry and Conservation Science
 .
Oxford University Press
.
Artioli
,
G.
and
Secco
,
M.
(
2016
)
Modern and ancient masonry: Nature and role of the binder
. Pp.
3
10
in:
Brick and Block Masonry – Trends, Innovations and Challenges
  (
C.
Modena
,
F.
Da Porto
and
M.R.
Valluzzi
, editors).
Proceedings of the 16th International Brick and Block Masonry Conference
,
Padova
, 26-30 June 2016.
Taylor & Francis Group
,
London
.
Artioli
,
G.
,
Nicola
,
C.
,
Montana
,
G.
,
Angelini
,
I.
,
Nodari
,
L.
and
Russo
,
U.
(
2009
)
The blue enamels in the baroque decorations of the churches of Palermo, Sicily: Fe2+-coloured glasses from lime kilns
.
Archaeometry
 ,
51
,
197
213
.
Artioli
,
G.
,
Cerulli
,
T.
,
Cruciani
,
G.
,
Dalconi
,
M.C.
,
Ferrari
,
G.
,
Parisatto
,
M.
,
Rack
,
A.
and
Tucoulou
,
R.
(
2010
)
X-ray diffraction microtomography (XRD-CT), a novel tool for non-invasive mapping of phase development in cement materials
.
Analytical and ioanalytical Chemistry
 ,
397
,
2131
2136
.
Artioli
,
G.
,
Valentini
,
L.
,
Dalconi
,
M.C.
,
Parisatto
,
M.
,
Voltolini
,
M.
,
Russo
,
V.
and
Ferrari
,
G.
(
2014a
)
Imaging of nano-seeded nucleation in cement pastes by X-ray diffraction tomography
.
International Journal of Materials Research
 ,
105
,
628
631
.
Artioli
,
G.
,
Valentini
,
L.
,
Voltolini
,
M.
,
Dalconi
,
M.C.
,
Ferrari
,
G.
and
Russo
,
V.
(
2014b
)
Direct imaging of nucleation mechanisms by synchrotron diffraction micro-tomography: superplasticizer-induced change of C–S–H nucleation in cement
.
Crystal Growth & Design
 ,
15
,
20
23
.
Ashby
,
M.F.
(
2013
)
Materials and the Environment: Eco-informed Material Choice
 .
Elsevier, Amsterdam and Butterworth-Heinemann,
Oxford.
Avrami
,
E.
,
Guillaud
,
H.
and
Hardy
M.
(editors) (
2008
)
Terra Literature Review. An Overview of Research in Earthen Architecture Conservation
 .
The Getty Conservation Institute
,
Los Angeles
.
Aygen
,
Z.
(
2013
)
International Heritage and Historic Building Conservation: Saving the World’s Past
  (Vol.
3)
.
Routledge
,
London
.
Barba
,
L.
,
Blancas
,
J.
,
Manzanilla
,
L.R.
,
Ortiz
,
A.
,
Barca
,
D.
,
Crisci
,
G.M.
,
Miriello
,
D.
and
Pecci
,
A.
(
2009
)
Provenance of the limestone used in Teotihuacan (Mexico): A methodological approach
.
Archaeometry
 ,
51
,
525
545
.
Barcelo
,
L.
,
Kline
,
J.
,
Walenta
,
G.
and
Gartner
,
E.
(
2014
)
Cement and carbon emissions
.
Materials and Structures
 ,
47
,
1055
1065
.
Baronio
,
G.
and
Binda
,
L.
(
1997
)
Study of the pozzolanicity of some bricks and clays
.
Construction and Building Materials
 ,
11
,
41
46
.
Bakolas
,
A.
,
Aggelakopoulou
,
E.
and
Moropoulou
,
A.
(
2008
)
Evaluation of pozzolanic activity and physico-mechanical characteristics in ceramic powder-lime pastes
.
Journal of Thermal Analysis and Calorimetry
 ,
92
,
345
351
.
Barnes
,
P.
and
Bensted
,
J.
(
2002
)
Structure and Performance of Cements
 .
CRC Press
,
Boca Raton, Florida, USA
.
Bar-Yosef
,
O.
(
1986
)
The walls of Jericho: An alternative interpretation
.
Current Anthropology
 ,
27
,
157
162
.
Bailey
,
S.W.
(
1988
)
Hydrous Phyllosilicates (Exclusive of Micas)
(
S.W.
Bailey
, editor).
Reviews in Mineralogy
 ,
19
.
Mineralogical Society of America
.
Chantilly, Virginia, USA
.
Bellotto
,
M.
and
Signes-Frehel
,
M.
(
1998
)
The Role of Powder X-ray Diffraction in the Cement Industry
.
European Powder Diffraction Conference
.
Materials Science Forum
 ,
Vols
.
278
281
.
Bellotto
,
M.
,
Gualtieri
,
A.
,
Artioli
,
G.
and
Clark
,
S.M.
(
1995
)
Kinetic study of the kaolinite-mullite reaction sequence. Part I: kaolinite dehydroxylation
.
Physics and Chemistry of Minerals
 ,
22
,
207
217
.
Bensted
,
J.
(
1999
)
A discussion of the paper “Use of cactus in mortars and concrete” by S. Chandra, L. Eklund, and R.R. Villarreal. – Authors’reply
.
Cement and Concrete Research
 ,
29
,
967
969
.
Bentur
,
A.
(
2002
)
Cementitious materials – Nine millennia and a new century: Past, present, and future. American Society of Civil Engineers, 150th Anniversary Paper
.
Journal of Materials in Civil Engineering
 , JAN/FEB
2002
,
2
22
.
Bequette
,
A.
and
Dhanjal
,
S.
(
2011
)
Continuous X-ray diffraction at the Buzzi Unicem festus plant
. Pp.
1
10
in:
Cement Industry Technical Conference, 2011 IEEE-IAS/PCA 53rd.
IEEE
.
Biton
,
R.
,
Goren
,
Y.
and
Goring-Morris
,
A.N.
(
2014
)
Ceramics in the Levantine Pre-Pottery Neolithic B: evidence from Kfar HaHoresh, Israel
.
Journal of Archaeological Science
 ,
41
,
740
748
.
Blauer-Bohm
,
C.
and
Jagers
,
E.
(
1997
)
Analysis and recognition of dolomitic lime mortars
. Pp.
223
235
in:
Roman Wall Painting: Materials, Techniques, Analysis and Conservation
  (
H.
Bearat
,
M.
Fuchs
,
M.
Maggetti
and
D.
Paunier
, editors).
Proceedings of the International Workshop
,
Fribourg
, 7–9 March 1996.
Institute of Mineralogy and Petrography
,
Fribourg, Germany
.
Blezard
,
R.G.
(
2003
)
The history of calcareous cements
. Pp.
1
19
in:
Lea’s Chemistry of Cement and Concrete
  (
P.C.
Hewlett
, editor).
Butterworth-Heinemann
,
Oxford, UK
.
Böke
,
H.
,
Akkurt
,
S.
,
İpekoğlu
,
B.
and
Uğurlu
,
E.
(
2006
)
Characteristics of brick used as aggregate in historic brick-lime mortars and plasters
.
Cement and Concrete Research
 ,
36
,
1115
1122
.
Bonetto
,
J.
,
Artioli
,
G.
,
Secco
,
M.
and
Addis
,
A.
(
2016
)
The use of the pozzolanic ashes in the big yards of Cisalpine Gaul during the Roman Republican Age: The cases of Aquileia and Ravenna
. Pp.
29
44
in:
Proceedings of the 5th International Workshop on the Archaeology of Roman Construction
(
S.
Camporeale
,
J.
DeLaine
and
A.
Pizzo
, editors).
Oxford
, 11-12 April 2015.
“Arqueología de la Construcción V. Manmade materials, engineering and infrastructure”
 .
CSIC
,
Madrid
.
Bonsall
,
C.
,
Radovanović
,
I.
,
Roksandic
,
M.
,
Cook
,
G.T.
,
Higham
,
T.
and
Pickard
,
C.
(
2008
)
Dating burial practices and architecture at Lepenski Vir
. Pp.
175
204
in:
The Iron Gates in Prehistory: New Perspectives
  (
C.
Bonsall
,
I.
Radovanović
: and
V.
Boroneanţ
, editors).
Archaeopress
,
Oxford, UK
.
Borić
,
D.
(
2002
)
The Lepenski Vir conundrum: reinterpretation of the Mesolithic and Neolithic sequences in the Danube Gorges
.
Antiquity
 ,
76
,
1026
1039
.
Brandon
,
C.
,
Hohlfelder
,
R.L.
,
Oleson
,
J.P.
and
Stern
,
C.
(
2005
)
The Roman Maritime Concrete Study (ROMACONS): the harbour of Chersonisos in Crete and its Italian connection
.
Méditerranée. Revue géographique des pays méditerranéens/Journal of Mediterranean Geography
 ,
104
,
25
29
.
Brandon
,
C.J.
,
Hohlfelder
,
R.L.
,
Jackson
,
M.D.
and
Oleson
,
J.P.
(
2014
)
Building for eternity: the history and technology of Roman concrete engineering in the sea
 .
Oxbow Books
.
Bras
,
A.
and
Henriques
,
F.M.
(
2012
)
Natural hydraulic lime based grouts–The selection of grout injection parameters for masonry consolidation
.
Construction and Building Materials
 ,
26
,
135
144
.
Brown
,
G.
and
Brindley
,
G.W.
(editors) (
1980
)
Crystal Structures of Clay Minerals and their X-ray Identification
 .
Monograph 5. Mineralogical Society of Great Britain & Ireland,
London.
Bullard
,
J.W.
,
Jennings
,
H.M.
,
Livingston
,
R.A.
,
Nonat
,
A.
,
Scherer
,
G.W.
,
Schweitzer
,
J.S.
,
Scrivener
,
K.L.
and
Thomas
,
J.J.
(
2011
)
Mechanisms of cement hydration
.
Cement and Concrete Research
 ,
41
,
1208
1223
.
Burg
,
A.
,
Starinsky
,
A.
,
Bartov
,
Y.
and
Kolodny
,
Y.
(
1991
)
Geology of the Hatrurim formation (“mottled zone”) in the Hatrurim basin
.
Israel Journal of Earth Sciences
 ,
40
,
107
124
.
Buyle
,
M.
,
Braet
,
J.
and
Audenaert
,
A.
(
2013
)
Life cycle assessment in the construction sector: A review
.
Renewable and Sustainable Energy Reviews
 ,
26
,
379
388
.
Callebaut
,
K.
,
Elsen
,
J.
,
Van Balen
,
K.
and
Viaene
,
W.
(
2000
)
Historical and scientific study of hydraulic mortars from the 19th century
. Pp.
125
132
in:
Proceedings of the International RILEM-workshop “Historic Mortars: Characteristics and Tests”
,
Paisley, UK
.
Callebaut
,
K.
,
Elsen
,
J.
,
Van Balen
,
K.
and
Viaene
,
W.
(
2001
)
Nineteenth century hydraulic restoration mortars in the Saint Michael’s Church (Leuven, Belgium): Natural hydraulic lime or cement?
Cement and Concrete Research
 ,
31
,
397
403
.
Cameron
,
M.A.S.
,
Jones
,
R.E.
and
Philippakis
,
S.E.
(
1977
)
Scientific analyses of Minoan fresco samples from Knossos
.
Annual of the British School at Athens
 ,
72
,
121
184
.
Cantisani
,
E.
,
Cecchi
,
A.
,
Chiaverini
,
I.
,
Fratini
,
F.
,
Manganelli Del Fá
,
C.
,
Pecchioni
,
E.
and
Rescic
,
S.
(
2002
)
The binder of the Roman concrete of the Ponte di Augusto at Narni (Italy)
.
Periodico di Mineralogia
 ,
71
,
113
123
.
Carran
,
D.
,
Hughes
,
J.
,
Leslie
,
A.
and
Kennedy
,
C.
(
2012
)
A short history of the use of lime as a building material beyond Europe and North America
.
International Journal of Architectural Heritage
 ,
6
,
117
146
.
Cazalla
,
O.
,
Rodriguez-Navarro
,
C.
,
Sebastian
,
E.
,
Cultrone
,
G.
and
Torre
,
M.J.
(
2000
)
Aging of lime putty: effects on traditional lime mortar carbonation
.
Journal of the American Ceramic Society
 ,
83
,
1070
1076
.
Chandra
,
S.
(
2002
)
Properties of concrete with mineral and chemical admixtures
. Pp.
140
185
in:
Structure and Performance of Cements
 . 2nd Edition. (
J.
Bensted
and
P.
Barnes
, editors).
Spon Press
,
London – NewYork.
Chandra
,
S.
and
Aavik
,
J.
(
1983
)
Influence of black gram (natural organic material) addition as admixture in cement mortar and concrete
.
Cement and Concrete Research
 ,
13
,
423
430
.
Chandra
,
S.
,
Eklund
,
L.
and
Villarreal
,
R.R.
(
1998
)
Use of cactus in mortars and concrete
.
Cement and Concrete Research
 ,
28
,
41
51
.
Charola
,
A.E.
,
Rodrigues
,
P.F.
,
McGhie
,
A.R.
and
Henriques
,
F.M.
(
2005
)
Pozzolanic components in lime mortars: Correlating behaviour, composition and microstructure
.
Restoration of Buildings and Monuments
 ,
11
,
111
118
.
Chatterjee
,
A.K.
(
2002
)
Special cements
. Pp.
186
236
in:
Structure and Performance of Cements
 . 2nd Edition (
J
Bensted
and
P.
Barnes
, editors).
Spon Press
,
London, New York
.
Chen
,
C.
,
Habert
,
G.
,
Bouzidi
,
Y.
,
Jullien
,
A.
and
Ventura
,
A.
(
2010
)
LCA allocation procedure used as an incitative method for waste recycling: An application to mineral additions in concrete
.
Resources, Conservation and Recycling
 ,
54
,
1231
1240
.
Cheung
,
J.
,
Jeknavorian
,
A.
,
Roberts
,
L.
and
Silva
,
D.
(
2011
)
Impact of admixtures on the hydration kinetics of Portland cement
.
Cement and Concrete Research
 ,
41
,
1289
1309
.
Chiarelli
,
N.
,
Miriello
,
D.
,
Bianchi
,
G.
,
Fichera
,
G.
,
Giamello
,
M.
and
Memmi Turbanti
,
I.
(
2015
)
Characterisation of ancient mortars from the S. Niccol archaeological complex in Montieri (Tuscany–Italy)
.
Construction and Building Materials
 ,
96
,
442
460
.
Chu
,
V.
,
Regev
,
L.
,
Weiner
,
S.
and
Boaretto
,
E.
(
2008
)
Differentiating between anthropogenic calcite in plaster, ash and natural calcite using infrared spectroscopy: implications in archaeology
.
Journal of Archaeological Science
 ,
35
,
905
911
.
Collepardi
,
M.
,
Collepardi
,
S.
and
Troli
,
R.
(
2007
)
Concrete Mix Design
.
Grafiche Tintoretto,
Lancenigo, Italy
.
Costa
,
U.
,
Gotti
,
E.
and
Tognon
,
G.
(
2000
)
Nota tecnica: malte prelevate da mura antiche dallo scavo della Banca Popolare di Ravenna
. Pp.
25
28
in:
Manzelli V. “Le mura di Ravenna repubblicana”
  (
L.
Quilici
, and
S.
Quilici Gigli
, editors).
“Fortificazioni antiche in Italia – Età Repubblicana”
 .
L’Erma di Bretschneider
,
Roma.
Coulson
,
W.
and
Wilkie
,
N.C.
(
1986
)
Ptolemaic and Roman kilns in the Western Nile delta
.
Bulletin of the American Schools of Oriental Research
 ,
263
,
61
75
.
Cultrone
,
G.
,
Sebastián
,
E.
,
Elert
,
K.
,
De la Torre
,
M.J.
,
Cazalla
,
O.
and
Rodriguez–Navarro
,
C.
(
2004
)
Influence of mineralogy and firing temperature on the porosity of bricks
.
Journal of the European Ceramic Society
 ,
24
,
547
564
.
Dalconi
,
M.C.
,
Favero
,
M.
and
Artioli
,
G.
(
2008
)
In-situ XRPD of hydrating cement with lab instrument: reflection vs. transmission measurements
.
Proc. EPDIC-11
,
Warsaw, Poland
, 18–22 September 2008.
Zeitschrift für Kristallographie, Proceedings
,
1
,
155
161
.
Damidot
,
D.
,
Lothenbach
,
B.
,
Herfort
,
D.
and
Glasser
,
F.P.
(
2011
)
Thermodynamics and cement science
.
Cement and Concrete Research
 ,
41
,
679
695
.
Damtoft
,
J.S.
,
Lukasik
,
J.
,
Herfort
,
D.
,
Sorrentino
,
D.
and
Gartner
,
E.M.
(
2008
)
Sustainable development and climate change initiatives
.
Cement and Concrete Research
 ,
38
,
115
127
.
Davidson
,
T.E.
and
McKerrell
,
H.
(
1976
)
Pottery analysis and Halaf Period trade in the Khabur Headwaters Region
.
Iraq
 ,
38
,
45
56
.
Day
,
K.
(
2003
)
Concrete Mix Design, Quality Control and Specification (with CD ROM)
.
CRC Press
,
Boca Raton, Florida, USA
.
De la Torre
,
A.G.
and
Aranda
,
M. G.
(
2003
)
Accuracy in Rietveld quantitative phase analysis of Portland cements
.
Journal of Applied Crystallography
 ,
36
,
1169
1176
.
Diekamp
,
A.
,
Stalder
,
R.
,
Konzett
,
J.
and
Mirwald
,
P.W.
(
2012
)
Lime mortar with natural hydraulic components: characterisation of reaction rims with FTIR imaging in ATR-mode
. Pp.
105
113
in:
Historic Mortars
 .
Springer
,
Dordrecht, The Netherlands
.
Dix
,
B.
(
1982
)
The manufacture of lime and its uses in the Western Roman provinces
.
Oxford Journal of Archaeology
 ,
1
,
331
346
.
Earl
,
J.
and
Saint
,
A.
(
2015
)
Building Conservation Philosophy
 .
Routledge
,
London
.
Edmeades
,
R.M.
and
Hewlett
,
P.C.
(
2003
)
Cement admixtures
. Pp.
841
906
in:
Lea’s Chemistry of Cement and Concrete
  (
P.C.
Hewlett
, editor).
Butterworth-Heinemann
,
Oxford, UK
.
El Ali
,
A.
,
Barbin
,
V.
,
Calas
,
G.
,
Cervelle
,
B.
,
Ramseyer
,
K.
and
Bouroulec
,
J.
(
1993
)
Mn2+-activated luminescence in dolomite, calcite and magnesite: quantitative determination of manganese and site distribution by EPR and CL spectroscopy
.
Chemical Geology
 ,
104
,
189
202
.
Elsen
,
J.
(
2004
)
Characterisation of binder related particles (lime lumps) in historic lime mortars
.
Proceedings of the 8th International Congress on Applied Mineralogy (ICAM2004)
,
Sao Paulo,
347
349
.
Elsen
,
J.
(
2006
)
Microscopy of historic mortars – A review
.
Cement and Concrete Research
 ,
36
,
1416
1424
.
Elsen
,
J.
,
Brutsaert
,
A.
,
Deckers
,
M.
and
Brulet
,
R.
(
2004
)
Microscopical study of ancient mortars from Tournai (Belgium)
.
Materials Characterization
 ,
53
,
289
294
.
Elsen
,
J.
,
Van Balen
,
K.
and
Mertens
,
G.
(
2012
)
Hydraulicity in historic lime mortars: a review
. Pp.
125
139
in:
Historic Mortars
 .
Springer
,
Dordrecht, The Netherlands
.
Fang
,
S.Q.
,
Zhang
,
H.
,
Zhang
,
B.J.
and
Zheng
,
Y.
(
2014
)
The identification of organic additives in traditional lime mortar
.
Journal of Cultural Heritage
 ,
15
,
144
150
.
Faria
,
P.
,
Henriques
,
F.
and
Rato
,
V.
(
2008
)
Comparative evaluation of lime mortars for architectural conservation
.
Journal of Cultural Heritage
 ,
9
,
338
346
.
Fernandez
,
R.
,
Martirena
,
F.
and
Scrivener
,
K.L.
(
2011
)
The origin of the pozzolanic activity of calcined clay minerals: A comparison between kaolinite, illite and montmorillonite
.
Cement and Concrete Research
 ,
41
,
113
122
.
Flatt
,
R.J.
,
Roussel
,
N.
and
Cheeseman
,
C.R.
(
2012
)
Concrete: An eco material that needs to be improved
.
Journal of the European Ceramic Society
 ,
32
,
2787
2798
Forsyth
,
M.
(editor) (
2007a
)
Understanding Historic Building Conservation
 .
John Wiley & Sons
,
New York
.
Forsyth
,
M.
(editor) (
2007b
)
Structures and Construction in Historic Building Conservation
 .
John Wiley & Sons
,
New York
.
Forsyth
,
M.
(editor) (
2008
)
Materials and Skills for Historic Building Conservation
 .
John Wiley & Sons
.
Frankeová
,
D.
,
Slížková
,
Z.
and
Drdácký
,
M.
, (
2012
)
Characteristics of mortars from ancient bridges
. Pp.
165
174
in:
Historic Mortars
 .
Springer
,
Dordrecht, The Netherlands
.
Franzini
,
M.
,
Leoni
,
L.
,
Lezzerini
,
M.
and
Sartori
,
F.
(
1999
)
On the binder of some ancient mortars
.
Mineralogy and Petrology
 ,
67
,
59
69
.
Franzini
,
M.
,
Leoni
,
L.
and
Lezzerini
,
M.
(
2000
)
A procedure for determining the chemical composition of binder and aggregate in ancient mortars: its application to mortars from some medieval buildings in Pisa
.
Journal of Cultural Heritage
 ,
1
,
365
373
.
Franzini
,
M.
,
Leoni
,
L.
,
Lezzerini
,
M.
and
Sartori
,
F.
(
2000
)
The mortar of the “Leaning Tower” of Pisa: the product of a medieval technique for preparing high-strength mortars
.
European Journal of Mineralogy
 ,
12
,
1151
1163
.
Fratini
,
F.
,
Pecchioni
,
E.
,
Rovero
,
L.
and
Tonietti
,
U.
(
2011
)
The earth in the architecture of the historical centre of Lamezia Terme (Italy): characterization for restoration
.
Applied Clay Science
 ,
53
,
509
516
.
Frierman
,
J.D.
(
1971
)
Lime burning as the precursor of fired ceramics
.
Israel Exploration Journal
 ,
21
,
212
216
.
Friesem
,
D.E.
,
Wattez
,
J.
and
Onfray
,
M.
(
2017
)
Earth construction materials
. Pp.
99
112
in:
Archaeological Soil and Sediment Micromorphology
  (
C.
Nicosia
and
G.
Stoops
, editors).
Wiley Blackwell
,
Hoboken, New Jersey, USA
.
Furlan
,
V.
and
Bissegger
,
P.
(
1975
)
Les mortiers anciens – Historie et essais d’analyse scientifiques
.
Zeitschrift fur Schweizerische Archaeologie und Kunstgeschichte
 ,
32
,
166
178
.
Garfinkel
,
Y.
(
1987
)
Burnt lime products and social implications in the Pre-Pottery Neolithic B villages of the Near East
.
Paléorient
 ,
13
,
69
76
.
Gartner
,
E.
and
Hirao
,
H.
(
2015
)
A review of alternative approaches to the reduction of CO2 emissions associated with the manufacture of the binder phase in concrete
.
Cement and Concrete Research
 ,
78
,
126
142
.
Gartner
,
E.M.
,
Young
,
J.F.
,
Damidot
,
D.A.
and
Jawed
,
I.
(
2002
)
Hydration of Portland cement
. Pp.
57
113
in:
Structure and Performance of Cements
 . 2nd Edition (
J.
Bensted
and
P.
Barnes
, editors).
Spon Press
,
London, New York
.
Ghosh
,
A.
(editor) (
1989
)
An Encyclopaedia of Indian Archaeology
 .
Brill
,
Amsterdam
.
Gibbs
,
K.
(
2015
)
Pottery invention and innovation in East Asia and the Near East
.
Cambridge Archaeological Journal
 ,
25
,
339
351
.
Gilat
,
A.
(
1998
)
Hydrothermal activity and hydro-explosions as a cause of natural combustion and pyrolysis of bituminous rocks; the case of Pliocene metamorphism in Israel (Hatrurim Formation)
.
Current Research – Geological Survey of Israel
 ,
11
,
96
102
.
Goldberg
,
P.
and
Bar-Yosef
,
O.
(
1998
)
Site formation processes in Kebara and Hayonim caves and their significance in Levantine prehistoric caves
. Pp.
107
126
in:
Neanderthals and Modern Humans in Western Asia
  (
T.
Akazawa
,
K.
Aoki
and
O.
Bar-Yosef
, editors).
Springer-Verlag
,
Berlin-New York
.
Goren
,
Y.
,
Goring-Morris
,
A.N.
and
Segal
,
I.
(
2001
)
The technology of skull modelling in the Pre-Pottery Neolithic B (PPNB): regional variability, the relation of technology and iconography and their archaeological implications
.
Journal of Archaeological Science
 ,
28
,
671
690
.
Gosselin
,
C.
,
Vergès-Belmin
,
V.
,
Royer
,
A.
and
Martinet
,
G.
(
2009
)
Natural cement and monumental restoration
.
Materials and Structures
 ,
42
,
749
763
.
Gotti
,
E.
,
Oleson
,
J.P.
,
Bottalico
,
L.
,
Brandon
,
C.
,
Cucitore
,
R.
and
Hohlfelder
,
R.L.
(
2008
)
A comparison of the chemical and engineering characteristics of ancient Roman hydraulic concrete with a modern reproduction of Vitruvian hydraulic concrete
.
Archaeometry
 ,
50
,
576
590
.
Gourdin
,
W.H.
and
Kingery
,
W.D.
(
1975
)
The beginning of pyrotechnology: Neolithic and Egyptian limeplaster
.
Journal of Field Archaeology
 ,
2
,
133
150
.
Greco
,
A.V.
(
2011
)
Virtutes materiae. Il contributo delle fonti latine nello studio di malte, intonaci e rivestimenti nel mondo romano
 .
Sandhi, Ortacesus
.
Griffin
,
P.S.
,
Grissom
,
C.A.
and
Rollefson
,
G.O.
(
1998
)
Three late eighth millennium plastered faces from ′Ain Ghazal, Jordan
.
Paléorient
 ,
24
,
59
70
.
Gualtieri
,
A.
,
Bellotto
,
M.
,
Artioli
,
G.
and
Clark
,
S.M.
(
1995
)
Kinetic study of the kaolinite-mullite reaction sequence. Part II: mullite formation
.
Physics and Chemistry of Minerals
 ,
22
,
215
222
.
Gualtieri
,
A.
and
Bellotto
,
M.
(
1998
)
Modelling the structure of the metastable phases in the reaction sequence kaolinite-mullite by X-ray scattering experiments
.
Physics and Chemistry of Minerals
 ,
25
,
442
452
.
Gulzar
,
S.
,
Chaudhry
,
M.N.
and
Burg
,
J.P.
(
2013
)
Chemical and mineralogical characterization of old mortars from Jahangir tomb, Lahore-Pakistan
.
Asian Journal of Chemistry
 ,
25
,
133
.
Hansen
,
E.F.
,
Rodriguez-Navarro
,
C.
and
Hansen
,
R.D.
(
1997
)
Incipient Maya burntlime technology: Characterization and chronological variations in Preclassic plaster, stucco and mortar at Nakbe, Guatemala
. Pp.
207
216
in:
Materials Issues in Art and Archaeology V
 . (
P.B.
Vandiver
,
J.R.
Druzik
,
J.F.
Merkel
and
J.
Stewart
, editors).
Materials Research Society
,
Pittsburgh, Pennsylvania, USA
.
Harutyunyan
,
V.S.
,
Kirchheim
,
A.P.
,
Monteiro
,
P.J.M.
,
Aivazyan
,
A.P.
and
Fischer
,
P.
(
2009
)
Investigation of early growth of calcium hydroxide crystals in cement solution by soft X-ray transmission microscopy
.
Journal of Materials Science
 ,
44
,
962
969
.
Hauptmann
,
A.
and
Yalcin
,
Ü.
(
2001
)
Lime plaster, cement and the first puzzolanic reaction
.
Paléorient
 ,
26
,
61
68
.
Heimann
,
R.B.
,
Maggetti
,
M.
,
Heiman
,
G.
and
Maggetti
,
J.
(
2010
)
Ancient and Historical Ceramics: Materials, Technology, Art and Culinary Traditions
 .
Schweizerbart Science Publishers,
Berlin
.
Herodotus
.
English translation by A.D. Godley
.
Harvard University Press
,
Cambridge, Massachusetts, USA; W. Heinemann, London.
1920
.
Hesse
,
C.
,
Goetz-Neunhoeffer
,
F.
and
Neubauer
,
J.
(
2011
)
A new approach in quantitative in-situ XRD of cement pastes: Correlation of heat flow curves with early hydration reactions
.
Cement and Concrete Research
 ,
41
,
123
128
.
Hewlett
,
P.
(
2003
)
Lea’s Chemistry of Cement and Concrete
 .
Butterworth-Heinemann
.
Hobbs
,
L.W.
and
Siddall
,
R.
(
2011
)
Cementitious materials of the ancient world
. Pp.
35
60
in:
Building Roma Aeterna
  (
Å.
Ringbom
and
R.L.
Hohlfelder
, editors) (
Proceedings
).
The Finnish Society of Sciences and Letters
,
Helsinki
.
Hodder
,
I.
(
2006
)
The Leopard’s Tale: Revealing the Mysteries of Çatalhöyük
 .
Thames & Hudson
,
London
.
Hodder
,
I.
(
2012
)
Entangled – An Archaeology of the Relationship between Humans and Things
 .
Wiley-Blackwell
.
Hong
,
S.Y.
and
Glasser
,
F.P.
(
2002
)
Alkali sorption by CSH and CASH gels: Part II. Role of alumina
.
Cement and Concrete Research
 ,
32
,
1101
1111
.
Huang
,
K.Z.
(
2003
)
Study and conservation of cultural architecture materials
.
Southeast Cult
 .,
173
,
93
96
.
Hughes
,
J.J.
,
Leslie
,
A.B.
and
Callebaut
,
K.
(
2001
)
The petrography of lime inclusions in historic lime based mortars
.
Proceedings of the 8th Euroseminar on Microscopy Applied to Building Materials
,
359
364
.
Huisman
,
D.J
and
Milek
,
K.B.
(
2017
)
Turf as construction material
. Pp.
113
136
in:
Archaeological Soil and Sediment Micromorphology
  (
C.
Nicosia
and
G.
Stoops
, editors).
Wiley Blackwell
,
Hoboken, New Jersey, USA
.
Hyman
,
D.S.
(
1970
)
Precolumbian cements: A study of the calcareous cements in Prehispanic Mesoamerican building construction
 . Ph.D. Dissertation,
Johns Hopkins University,
Baltimore, Maryland, USA
.
Hyslop
,
J.
(
2014
)
Inka Settlement Planning
 .
University of Texas Press
.
Isebaert
,
A.
,
Van Parys
,
L.
and
Cnudde
,
V.
(
2014
)
Composition and compatibility requirements of mineral repair mortars for stone – A review
.
Construction and Building Materials
 ,
59
,
39
50
.
Jackson
,
M.D.
,
Marra
,
F.
,
Deocampo
,
D.
,
Vella
,
A.
,
Kosso
,
C.
and
Hay
,
R.
(
2007
)
Geological observations of excavated sand (harenae fossiciae) used as fine aggregate in ancient Roman pozzolanic mortars
.
Journal of Roman Archaeology
 ,
20
,
1
30
.
Jackson
,
M.D.
,
Vola
,
G.
,
Všianský
,
D.
,
Oleson
,
J.P.
,
Scheetz
,
B.E.
,
Brandon
,
C.
and
Hohlfelder
,
R.L.
(
2012
)
Cement microstructures and durability in ancient Roman seawater concretes
. Pp.
49
76
in:
Historic Mortars
 .
Springer
,
Dordrecht, The Netherlands
.
Jackson
,
M.D.
,
Chae
,
S.R.
,
Mulcahy
,
S.R.
,
Meral
,
C.
,
Taylor
,
R.
,
Li
,
P.
,
Emwas
,
A.-H.
,
Moon
,
J.
,
Yoon
,
S.
,
Vola
,
G.
,
Wenk
,
H.R.
and
Monteiro
,
P.J.M.
(
2013
)
Unlocking the secrets of Al-tobermorite in Roman seawater concrete
.
American Mineralogist
 ,
98
,
1669
1687
.
Jackson
,
M.D.
,
Mulcahy
,
S.R.
,
Chen
,
H.
,
Li
,
Y.
,
Li
,
Q.
,
Cappelletti
,
P.
and
Wenk
,
H.R.
(
2017
)
Phillipsite and Al-tobermorite mineral cements produced through low-temperature water-rock reactions in Roman marine concrete
.
American Mineralogist
 ,
102
,
1435
1450
.
Jansen
,
D.
,
Goetz-Neunhoeffer
,
F.
,
Lothenbach
,
B.
and
Neubauer
,
J.
(
2012
)
The early hydration of Ordinary Portland Cement (OPC): An approach comparing measured heat flow with calculated heat flow from QXRD
.
Cement and Concrete Research
 ,
42
,
134
138
.
Jiang
,
M.
,
Chen
,
X.
,
Rajabipour
,
F.
and
Hendrickson
,
C.T.
(
2014
)
Comparative life cycle assessment of conventional, glass powder, and alkali-activated slag concrete and mortar
.
Journal of Infrastructure Systems
 ,
20
,
04014020
.
Karkanas
,
P.
(
2007
)
Identification of lime plaster in prehistory using petrographic methods: A review and reconsideration of the data on the basis of experimental and case studies
.
Geoarchaeology
 ,
22
,
775
796
.
Karkanas
,
P.
and
Goldberg
,
P.
(
2007
)
Micromorphology of sediments: Deciphering archaeological context
.
Israel Journal of Earth Sciences
 ,
56
,
63
71
.
Karkanas
,
P.
and
Efstratiou
,
N.
(
2009
)
Floor sequences in Neolithic Makri, Greece: micromorphology reveals cycles of renovation
.
Antiquity
 ,
83
,
955
967
.
Karkanas
,
P.
and
Stratouli
,
G.
(
2008
)
Neolithic lime plastered floors in Drakaina Cave, Kephalonia Island, Western Greece: Evidence of the significance of the site
.
Annual of the British School at Athens
 ,
103
,
27
41
.
Kenoyer
,
J.M.
(
1991
)
The Indus Valley Tradition of Pakistan and Western India
.
Journal of World Prehistory
 ,
5
,
331
385
.
Kenyon
,
K.M.
(
1981
)
Excavations at Jericho III. The Architecture and Stratigraphy of the Tell
 .
British School of Archaeology in Jerusalem
,
London
,
540 pp
.
Khan
,
A.
and
Lemmen
,
C.
(
2013
)
Bricks and urbanism in the Indus Civilization
.
arXiv preprint arXiv:1303.1426
 .
Khoury
,
H.N.
,
Salameh
,
E.
,
Clark
,
I.D.
,
Fritz
,
P.
,
Bajjali
,
W.
,
Milodowski
,
A.E.
,
Cave
,
M.R.
and
Alexander
,
W.R.
(
1992
)
A natural analogue of high pH cement pore waters from the Maqarin area of northern Jordan. I: introduction to the site
.
Journal of Geochemical Exploration
 ,
46
,
117
132
.
Kingery
,
D.W.
,
Vandiver
,
P.B.
and
Prickett
,
M.
(
1988
)
The beginnings of pyrotechnology, part II: Production and use of lime and gypsum plaster in the Pre-Pottery Neolithic Near East
.
Journal of Field Archaeology
 ,
15
,
219
243
.
Kingery
,
W.D.
,
Vandiver
,
P.B.
and
Noy
,
T.
(
1992
)
8,500-year-old sculpted plaster head from Jericho (Israel)
.
Materials Research Society Bulletin
 ,
17
,
46
52
.
Kopelson
,
E.
(
1996
)
Analysis and consolidation of architectural plasters from Çatalhöyük, Turkey
.
Master’s Thesis
 ,
University of Pennsylvania
,
USA
.
Kosednar-Legenstein
,
B.
,
Dietzel
,
M.
,
Leis
,
A.
and
Stingl
,
K.
(
2008
)
Stable carbon and oxygen isotope investigation in historical lime mortar and plaster–Results from field and experimental study
.
Applied Geochemistry
 ,
23
,
2425
2437
.
Koui
,
M.
and
Ftikos
,
C.
(
1998
)
The ancient Kamirian water storage tank: A proof of concrete technology and durability for three millenniums
.
Materials and Structures
 ,
31
,
623
627
.
Kozlowski
,
S.K.
and
Kempisty
,
A.
(
1990
)
Architecture of the Pre-Pottery Neolithic settlement in Nemrik, Iraq
.
World Archaeology
 ,
21
,
348
362
.
Kropáč
,
K.
and
Dolníček
,
Z.
(
2013
)
Non-metallurgical Slags in the Masonry of Obřany Castle in the Czech Republic: Evidence for the Local Production of Hydraulic Lime in the 14th Century?
Geoarchaeology
 ,
28
,
544
556
.
Kumar
,
K.
(
1984
)
The evidence of white-wash, plaster and pigment on North Indian sculpture with special reference to Sarnath
.
Artibus Asiae
 ,
45
,
199
206
.
Kurtis
,
K.E.
(
2015
)
Innovations in cement-based materials: Addressing sustainability in structural and infrastructure applications
.
Materials Research Society Bulletin
 ,
40
,
1102
1109
.
Kuzmin
,
Y.V.
(
2006
)
Chronology of the earliest pottery in East Asia: progress and pitfalls
.
Antiquity
 ,
80
,
362
371
.
L’Hôpital
,
E.
,
Lothenbach
,
B.
,
Le Saout
,
G.
,
Kulik
,
D.
and
Scrivener
,
K.
(
2015
)
Incorporation of aluminium in calcium-silicate-hydrates
.
Cement and Concrete Research
 ,
75
,
91
103
.
L’Hôpital
,
E.
,
Lothenbach
,
B.
,
Scrivener
,
K.
and
Kulik
,
D.A.
(
2016
)
Alkali uptake in calcium alumina silicate hydrate (CASH)
.
Cement and Concrete Research
 ,
85
,
122
136
.
Lamprecht
,
H.O.
(
1996
)
Opus caementitium: Bautechnik der Römer
 .
Beton-Verlag
,
Germany
.
Lancaster
,
L.C.
(
2005
)
Concrete Vaulted Construction in Imperial Rome: innovations in Context
 .
Cambridge University Press
,
Cambridge, Cambridge, UK
.
Lancaster
,
L.C.
(
2011
)
The use of lightweight concrete in Rome, Cilicia, and Tunisia
. Pp.
60
72
in:
Building Roma Aeterna
 
(Å.
Ringbom
and
R.L.
Hohlfelder
, editors). (
Proceedings) The Finnish Society of Sciences and Letters
,
Helsinki
.
Lancaster
,
L.C.
(
2012
)
Ash mortar and vaulting tubes: agricultural production and the building industry in North Africa
. Pp.
145
160
in:
Arqueología de la construcción III: Los procesos constructivos en el mundo romano: la economía de las obras
 . (
S.
Camporeale
,
H.
Dessales
and
A.
Pizzo
, editors).
Instituto de Arqueología de Merida
,
Madrid
.
Lancaster
,
L.C.
(
2015
)
Innovative Vaulting in the Architecture of the Roman Empire: 1st to 4th Centuries CE
 .
Cambridge University Press
,
Cambridge, UK
.
Lancaster
,
L.C.
,
Sottili
,
G.
,
Marra
,
F.
and
Ventura
,
G.
(
2010
)
Provenancing of lightweight volcanic stones used in ancient Roman concrete vaulting: Evidence from Turkey and Tunisia
.
Archaeometry
 ,
52
,
949
961
.
Lancaster
,
L.C.
,
Sottili
,
G.
,
Marra
,
F.
and
Ventura
,
G.
(
2011
)
Provenancing of lightweight volcanic stones used in ancient Roman concrete vaulting: evidence from Rome
.
Archaeometry
 ,
53
,
707
727
.
Laws
,
W.D.
(
1962
)
An investigation of temple plasters from Tikal, Guatemala, with evidence of the use by the ancient Maya of plant extracts in plaster making
.
Wrightia
 ,
2
,
5217
5228
.
Lechtman
,
H.K.
and
Hobbs
,
L.W.
(
1987
)
Roman concrete and the roman architectural revolution, ceramics and civilization
.
High-Technology Ceramics–Past, Present, and Future
 ,
3
,
81
128
.
Leslie
,
A.B.
and
Hughes
,
J.J.
(
2002
)
Binder microstructure in lime mortars: implications for the interpretation of analysis results
.
Quarterly Journal of Engineering Geology and Hydrogeology
 ,
35
,
257
263
.
Liew
,
K.M.
,
Sojobi
,
A.O.
and
Zhang
,
L.W.
(
2017
)
Green concrete: Prospects and challenges
.
Construction and Building Materials
 ,
156
,
1063
1095
.
Lindroos
,
A.
,
Heinemeier
,
J.
,
Ringbom
,
Å.
,
Brock
,
F.
,
Sonck-Koota
,
P.
,
Pehkonen
,
M.
and
Suksi
,
J.
(
2011
)
Problems in radiocarbon dating of Roman pozzolana mortars
. Pp.
214
230
in:
Building Roma Aeterna
 .
(Å.
Ringbom
and
R.L.
Hohlfelder
, editors). (
Proceedings) The Finnish Society of Sciences and Letters
,
Helsinki
.
Lindqvist
,
J.E.
and
Sandström
,
M.
(
2000
)
Quantitative analysis of historical mortars using optical microscopy
.
Materials and Structures
 ,
33
,
612
617
.
Littmann
,
E.R.
(
1957
)
Ancient Mesoamerican mortars, plasters, and stuccos: Comalcalco, part I
.
American Antiquity
 ,
23
,
135
140
.
Littmann
,
E.R.
(
1960
)
Ancient Mesoamerican mortars, plasters, and stuccos: The use of bark extracts in lime plasters
.
American Antiquity
 ,
25
,
593
597
.
Livingston
,
R.A.
(
1970
)
Materials analysis of the masonry of the Hagia Sophia Basilica, Istanbul
.
WIT Transactions on the Built Environment
 ,
4
,
15
31
.
Lothenbach
,
B.
,
Scrivener
,
K.
and
Hooton
,
R.D.
(
2011
)
Supplementary cementitious materials
.
Cement and Concrete Research
 ,
41
,
1244
1256
.
Macdonald
,
S.
(editor) (
2008
)
Concrete: Building Pathology
 .
John Wiley & Sons
,
Hoboken, New Jersey, USA
.
Machel
,
H.G.
,
Mason
,
R.A.
,
Mariano
,
A.N.
and
Mucci
,
A.
(
1991
)
Causes and emission of luminescence in calcite and dolomite
. In:
Luminescence Microscopy: Quantitative and Qualitative Aspects
 . (
C.E.
Barker
and
O.C.
Kopp
, editors).
Special Publication, SC25. SEPM
,
Tulsa, Oklahoma, USA
.
Mackay
,
E.J.H.
(
1938
)
Further Excavations at Mohenjo-Daro
 .
Government of India Press
,
New Delhi
,
162 pp
.
Magaloni
,
D.
,
Pancella
,
R.
,
Fruh
,
Y.
,
Canetas
,
J.
and
Castano
,
V.
(
1995
)
Studies on the Mayan mortars technique
. Pp.
483
489
in:
Materials Issues in Art and Archaeology IV
  (
P.B.
Vandiver
,
J.R.
Druzik
,
J.L.G.
Madrid
,
I.C.
Freestone
and
G.S.
Wheeler
, editors).
Materials Research Society
,
Pittsburgh, Pennsylvania, USA
.
Mahasenan
,
N.
,
Smith
,
S.
,
Humphreys
,
K.
and
Kaya
,
Y.
(
2003
)
The cement industry and global climate change: current and potential future cement industry CO2 emissions
. Pp.
995
1000
in:
Greenhouse Gas Control Technologies-6th International Conference
(Vol.
2
).
Elsevier
,
Amsterdam
.
Malhotra
,
V.M.
and
Mehta
,
P.K.
(
1996
)
Pozzolanic and Cementitious Materials
 . Vol.
1
.
Taylor & Francis
,
Abingdon, UK
.
Malinowski
,
R.
and
Garfinkel
,
Y.
(
1991
)
Prehistory of concrete
.
Concrete International
 ,
13
,
62
68
.
Manias
,
C.
,
Retallack
,
D.
and
Madsen
,
I.
(
2000
)
XRD for On-line Analysis and Control
.
World Cement
 , Feb 2000.
Maravelaki-Kalaitzaki
,
P.
,
Bakolas
,
A.
and
Moropoulou
,
A.
(
2003
)
Physico-chemical study of Cretan ancient mortars
.
Cement and Concrete Research
 ,
33
,
651
661
.
Maravelaki-Kalaitzaki
,
P.
,
Bakolas
,
A.
,
Karatasios
,
I.
and
Kilikoglou
,
V.
(
2005
)
Hydraulic lime mortars for the restoration of historic masonry in Crete
.
Cement and Concrete Research
 ,
35
,
1577
1586
.
Marra
,
F.
,
d’Ambrosio
,
E.
,
Gaeta
,
M.
and
Mattei
,
M.
(
2016
)
Petrochemical identification and insights on chronological employment of the volcanic aggregates used in ancient roman mortars
.
Archaeometry
 ,
58
,
177
200
.
Masoumi
,
M.M.
,
Banakar
H.
and
Boroomand
,
B.
(
2015
)
Review of ancient Persian lime mortar “Sarooj”
.
Malaysian Journal of Civil Engineering
 ,
27
,
94
109
.
Massazza
,
F.
(
1998
)
Pozzolana and pozzolanic cements
. Pp.
471
635
in:
Lea’s Chemistry of Cement and Concrete
 . 4th Edition (
P.C.
Hewlett
, editor).
Butterworth-Heimann,
Oxford, UK
.
Matschei
,
T.
,
Lothenbach
,
B.
and
Glasser
,
F.P.
(
2007
)
Thermodynamic properties of Portland cement hydrates in the system CaO–Al2O3–SiO2–CaSO4–CaCO3–H2O
.
Cement and Concrete Research
 ,
37
,
1379
1410
.
Maurenbrecher
,
A.P.
(
2004
)
Mortars for repair of traditional masonry
.
Practice Periodical on Structural Design and Construction
 ,
9
,
62
65
.
McCown
,
D.E.
(
1952
)
Excavations at Nippur, 1948–50
.
Journal of Near Eastern Studies
 ,
11
,
169
176
.
Merlini
,
M.
,
Artioli
,
G.
,
Meneghini
,
C.
,
Cerulli
,
T.
,
Bravo
,
A.
and
Cella
,
F.
(
2007
)
The early hydration and the set of Portland cements: in situ X-ray powder diffraction studies
.
Powder Diffraction
 ,
22
,
201
208
.
Merlini
,
M.
,
Artioli
,
G.
,
Cerulli
,
T.
,
Cella
,
F.
and
Bravo
,
A.
(
2008
)
Tricalcium aluminate hydration in additivated systems. A crystallographic study by SR–XRPD
.
Cement and Concrete Research
 ,
38
,
477
486
.
Milevski
,
I.
,
Khalaily
,
H.
,
Getzov
,
N.
and
Hershkovitz
,
I.
(
2008
)
The plastered skulls and other PPNB finds from Yiftahel, Lower Galilee (Israel)
.
Paléorient
 ,
34
,
37
46
.
Minke
,
G.
(
2012
)
Building with Earth: Design and Technology of a Sustainable Architecture
 .
Walter de Gruyter
,
Boston, Massachusetts, USA
.
Miriello
,
D.
,
Barba
,
L.
,
Blancas
,
J.
,
Bloise
,
A.
,
Cappa
,
M.
,
Cura
,
M.
,
De Angelis
,
D.
,
De Luca
,
R.
,
Pecci
,
A.
,
Taranto
,
M.
and
Yavuz
,
H.B.
(
2017
)
New compositional data on ancient mortars from Hagia Sophia (Istanbul, Turkey)
.
Archaeological and Anthropological Sciences
 ,
9
,
499
514
.
Mogetta
,
M.
(
2015
)
A new date for concrete in Rome
.
The Journal of Roman Studies
 ,
105
,
1
40
.
Montana
,
G.
,
Randazzo
,
L.
,
Cerniglia
,
M.R.
,
Aleo Nero
,
C.
and
Spatafora
,
F.
(
2016
)
Production technology of Early-Hellenistic lime-based mortars originating from a Punic-Roman residential area in Palermo (Sicily)
.
International Journal of Conservation Science
 ,
7
,
797
812
.
Monteiro
,
P.J.M.
,
Mancio
,
M.
,
Kirchheim
,
A.P.
,
Chae
,
R.
,
Ha
,
J.
,
Fischer
,
P.
and
Tyliszczak
,
T.
(
2011
)
Soft X-ray microscopy of green cements
. In:
AIP Conference Proceedings
(Vol.
1365
, No. 1, pp.
351
356
).
American Institute of Physics
,
College Park, Maryland, USA
.
Moorey
,
P.R.S.
(
1999
)
Ancient Mesopotamian Materials and Industries: The Archaeological Evidence
 .
Eisenbrauns
,
Warsaw, Indiana, USA
.
Mora
,
E.P.
(
2007
)
Life cycle, sustainability and the transcendent quality of building materials
.
Building and Environment
 ,
42
,
1329
1334
.
Moropoulou
,
A.
,
Bakolas
,
A.
and
Bisbikou
,
K.
(
2000
)
Investigation of the technology of historic mortars
.
Journal of Cultural Heritage
 ,
1
,
45
58
.
Moropoulou
,
A.
,
Cakmak
,
A.S.
,
Biscontin
,
G.
,
Bakolas
,
A.
and
Zendri
,
E.
(
2002
)
Advanced Byzantine cement based composites resisting earthquake stresses: the crushed brick and lime mortars of Justinian’s Hagia Sophia
.
Construction and Building Materials
 ,
16
,
543
552
.
Moropoulou
,
A.
,
Bakolas
,
A.
and
Anagnostopoulou
,
S.
(
2005
)
Composite materials in ancient structures
.
Cement and Concrete Composites
 ,
27
,
295
300
.
Oates
,
D.
(
1961
)
The excavations at Nimrud (Kalu), 1960
.
Iraq
 ,
23
,
1
14
.
Oates
,
D.
(
1990
)
Innovations in mud-bricks: decorative and structural techniques in ancient Mesopotamia
.
World Archaeology
 ,
21
,
388
406
.
Oates
,
J.A.H.
(
1998
)
Lime and Limestone: Chemistry and Technology, Production and Uses
 .
Wiley–VCH,
Weinheim, Germany
.
Odler
,
I.
(editor) (
2000
)
Special Inorganic Cements
 .
Spon Press
,
London, New York
.
Oleson
,
J.P.
(
2011
)
Harena sine calce: Building disasters, incompetent architects, and construction fraud in ancient Rome
. Pp.
9
27
in:
Building Roma Aeterna
 .
(Å.
Ringbom
and
R.L.
Hohlfelder
, editors). (
Proceedings) The Finnish Society of Sciences and Letters
,
Helsinki
.
Oleson
,
J.P.
,
Bottalico
,
L.
,
Brandon
,
C.
,
Cucitore
,
R.
,
Gotti
,
E.
and
Hohlfelder
,
R.L.
(
2006
)
Reproducing a Roman maritime structure with Vitruvian pozzolanic concrete
.
Journal of Roman Archaeology
 ,
19
,
31
52
.
Oppenheim
,
L.A.
(
1965
)
On royal gardens in Mesopotamia
.
Journal of Near Eastern Studies
 ,
24
,
328
333
.
Organ
,
R.M.
(
1961
)
The conservation of cuneiform tablets
.
The British Museum Quarterly
 ,
23
,
52
58
.
Ouellet-Plamondon
,
C.
and
Habert
,
G.
(
2015
)
Life cycle assessment (LCA) of alkali-activated cements and concretes
. Pp.
663
686
in:
Handbook of Alkali-activated Cements, Mortars and Concretes
 . (
F.
Pacheco-Torgal
,
J.
Labrincha
,
C.
Leonelli
,
A.
Palomo
and
P.
Chindaprasit
, editors).
Elsevier
,
Amsterdam
.
Pacheco-Torgal
,
F.
,
Labrincha
,
J.
,
Leonelli
,
C.
,
Palomo
,
A.
and
Chindaprasit
,
P.
(editors) (
2015
)
Handbook of Alkali-activated Cements, Mortars and Concretes
 .
Elsevier
,
Amsterdam
.
Papadimitriou
,
G.
and
Kordatos
,
J.
(
1993
)
The brown waterproofing plaster of the ancient cisterns in Laurion and its weathering and degradation
. Pp.
277
284
in:
ASMOSIA (Association for the Study of Marble and Other Stones used in Antiquity) Proc. 3rd International Conference.
Parisatto
M.
,
Dalconi
M.C.
,
Valentini
L.
,
Artioli
G.
,
Rack
A.
,
Tucoulou
R.
,
Cruciani
G.
and
Ferrari
G.
(
2015
)
Examining microstructural evolution of Portland cements by in situ synchrotron micro-tomography
.
Journal of Materials Science
 ,
50
,
1805
1817
.
Pecchioni
,
E.
,
Fratini
,
F.
and
Cantisani
,
E.
(
2006
)
The ancient mortars, an attestation of the material culture: the case of Florence
.
Periodico di Mineralogia
 ,
75
,
255
262
.
Pecchioni
,
E.
,
Fratini
,
F.
and
Cantisani
,
E.
(
2014
)
Atlas of the Ancient Mortars in Thin Section under the Optical Microscope
.
Kermes quaderni
 ,
Nardini Editore
,
Florence, Italy
.
Pedelì
,
C.
and
Pulga
,
S.
(
2013
)
Conservation Practices in Archaeological Excavations: Principles and Methods
 .
The Getty Conservation Institute
,
Los Angeles, California, USA
.
Pesce
,
G.L.
,
Ball
,
R.J.
,
Quarta
,
G.
and
Calcagnile
,
L.
(
2012
)
Identification, extraction, and preparation of reliable lime samples for 14C dating of plasters and mortars with the “Pure Lime Lumps” technique
.
Radiocarbon
 ,
54
,
933
942
.
Poduska
,
K.M.
,
Regev
,
L.
,
Berna
,
F.
,
Mintz
,
E.
,
Milevski
,
I.
,
Khalaily
,
H.
,
Weiner
,
S.
and
Boaretto
,
E.
(
2012
)
Plaster characterization at the PPNB site of Yiftahel (Israel) including the use of 14 C: implications for plaster production, preservation, and dating
.
Radiocarbon
 ,
54
,
887
896
.
Potts
,
D.T.
(
2014
)
Elamite Monumentality and Architectural Scale. Lessons from Susa and Choga Zanbil
. Pp.
23
38
in:
Approaching Monumentality in Archaeology
  (
J.F.
Osborne
, editor).
IEMA
Proceedings
, Vol.
3
.
State University of New York Press
.
Prescott
,
W.H.
(
1847
)
The Conquest of Peru
 .
Harper & Brothers (reprinted 2007, Digital Antiquaria).
Provis
,
J.L.
and
Van Deventer
,
J.S.J.
(editors) (
2009
)
Geopolymers: Structures, Processing, Properties and Industrial Applications
 .
Elsevier
,
Amsterdam
.
Provis
,
J.L
and
Van Deventer
,
J.S.J
(editors) (
2014
)
Alkali activated materials
 . State-of-the-Art Report, RILEM TC 224-AAM,
Springer
,
Berlin
.
Radovanović
,
I.
(
1996
)
The Iron Gates Mesolithic
 .
International Monographs in Prehistory
.
Ann Arbor, Michigan, USA
.
Radovanović
,
I.
(
2000
)
Houses and burials at Lepenski Vir
.
European Journal of Archaeology
 ,
3
,
330
349
.
Rao
,
H.
,
Li
,
B.
,
Yang
,
Y.
,
Ma
,
Q.
and
Wang
,
C.
(
2015
)
Proteomic identification of organic additives in the mortars of ancient Chinese wooden buildings
.
Analytical Methods
 ,
7
,
143
149
.
Redman
,
C.
(
1999
)
Human Impact on Ancient Environments
 .
University of Arizona Press
,
Tucson, Arizona, USA
.
Regev
,
L.
,
Zukerman
,
A.
,
Hitchcock
,
L.
,
Maeir
,
A.M.
,
Weiner
,
S.
and
Boaretto
,
E.
(
2010a
)
Iron age hydraulic plaster from Tell es-Safi/Gath, Israel
.
Journal of Archaeological Science
 ,
37
,
3000
3009
.
Regev
,
L.
,
Poduska
,
K.M.
,
Addadi
,
L.
,
Weiner
,
S.
and
Boaretto
,
E.
(
2010b
)
Distinguishing between calcites formed by different mechanisms using infrared spectrometry: archaeological applications
.
Journal of Archaeological Science
 ,
37
,
3022
3029
.
Reza
,
H.
(
2008
)
Bengal Gupta Viharas: Did such a phenomenon exist?
The International Journal of Interdisciplinary Social Sciences
 ,
3
,
211
216
.
Riccardi
,
M.P.
,
Lezzerini
,
M.
,
Car
,
F.
,
Franzini
,
M.
and
Messiga
,
B.
(
2007
)
Microtextural and microchemical studies of hydraulic ancient mortars: two analytical approaches to understand pre-industrial technology processes
.
Journal of Cultural Heritage
 ,
8
,
350
360
.
Richardson
,
I.G.
(
1999
)
The nature of CSH in hardened cements
.
Cement and Concrete Research
 ,
29
,
1131
1147
.
Richardson
,
I.G.
(
2004
)
Tobermorite/jennite-and tobermorite/calcium hydroxide-based models for the structure of CSH: applicability to hardened pastes of tricalcium silicate, β-dicalcium silicate, Portland cement, and blends of Portland cement with blast-furnace slag, metakaolin, or silica fume
.
Cement and Concrete Research
 ,
34
,
1733
1777
.
Rivera-Villarreal
,
R.
and
Krayer
,
S.
(
1996
)
Ancient structural concrete in Mesoamerica
.
Concrete International
 ,
18
,
67
70
.
Robson
,
E.
(
1996
)
Building with bricks and mortar
. In:
Houses and Households in Ancient Mesopotamia
  (
K.
Veenhof
, editor).
Leiden, The Netherlands
.
Rodriguez-Navarro
,
C.
,
Hansen
,
E.
and
Ginell
,
W.S.
(
1998
)
Calcium hydroxide crystal evolution upon aging of lime putty
.
Journal of the American Ceramic Society
 ,
81
,
3032
3034
.
Rodriguez-Navarro
,
C.
,
Ruiz-Agudo
,
E.
,
Luque
,
A.
,
Rodriguez-Navarro
,
A.B.
and
Ortega-Huertas
,
M.
(
2009
)
Thermal decomposition of calcite: mechanisms of formation and textural evolution of CaO nanocrystals
.
American Mineralogist
 ,
94
,
578
593
.
Rodriguez-Navarro
,
C.
,
Ruiz-Agudo
,
E.
,
Burgos-Cara
,
A.
,
Elert
,
K.
and
Hansen
,
E.F.
(
2017
)
Crystallization and colloidal stabilization of Ca(OH)2 in the presence of nopal juice (Opuntia ficus indica): Implications in architectural heritage conservation
.
Langmuir
 ,
33
,
10936
10950
.
Rollefson
,
G.O.
and
Kohler-Rollefson
,
I.
(
1992
)
Early Neolithic exploitation patterns in the Levant: Cultural impact on the environment
.
Population and Environment: A Journal of Interdisciplinary Studies
 ,
13
,
243
254
.
Ruiz-Agudo
,
E.
and
Rodriguez-Navarro
,
C.
(
2009
)
Microstructure and rheology of lime putty
.
Langmuir
 ,
26
,
3868
3877
.
Sanizadeh
,
S.K.
(
2008
)
Novel hydraulic structures and water management in Iran: a historical perspective
.
Options Mediterraneennes
 ,
83
,
26
43
.
Sauvage
,
M.
(
2011
)
Construction work in Mesopotamia in the time of the third Dynasty of Ur: Archaeological and textual evidence
. Pp.
40
50
in:
TerrAsia 2011
  (
H.
Wang
,
S.
Kim
,
H.
Guillaud
and
D.
Gandreau
, editors).
Proceedings of the 2011 International Conference on Earthen Architecture in Asia
,
Mokpo, Terrakorea
.
Schlegel
,
M.C.
,
Sarfraz
,
A.
,
Müller
,
U.
,
Panne
,
U.
and
Emmerling
,
F.
(
2012
)
First seconds in a building’s life – In situ synchrotron X-ray diffraction study of cement hydration on the millisecond timescale
.
Angewandte Chemie International Edition
 ,
51
,
4993
4996
.
Schmandt-Besserat
,
D.
(
1977
)
The earliest uses of clay in Syria
.
Expedition
 ,
19
,
28
.
Schneider
,
M.
,
Romer
,
M.
,
Tschudin
,
M.
and
Bolio
,
H.
(
2011
)
Sustainable cement production–present and future
.
Cement and Concrete Research
 ,
41
,
642
650
.
Schueremans
,
L.
,
Cizer
,
Ö.
,
Janssens
,
E.
,
Serré
,
G.
and
Van Balen
,
K.
(
2011
)
Characterization of repair mortars for the assessment of their compatibility in restoration projects: research and practice
.
Construction and Building Materials
 ,
25
,
4338
4350
.
Scrivener
,
K.
and
Favier
,
A.
(
2015
)
Calcined clays for sustainable concrete
.
RILEM series
 ,
Springer
,
Berlin
.
Scrivener
,
K.
,
Snellings
,
R.
and
Lothenbach
,
B.
(editors) (
2016
)
A Practical Guide to Microstructural Analysis of Cementitious Materials
 .
CRC Press
,
Boca Raton, Florida, USA
.
Secco
,
M.
,
Peruzzo
,
L.
,
Palasse
,
L.
,
Artioli
,
G.
,
Viani
,
A.
and
Gualtieri
,
A.F.
(
2014
)
Crystal chemistry of clinker relicts from aged cementitious materials
.
Journal of Applied Crystallography
 ,
47
,
1626
1637
.
Secco
,
M.
,
Dilaria
,
S.
,
Addis
,
A.
,
Bonetto
,
J.
,
Artioli
,
G.
and
Salvadori
,
M.
(
2018
)
The evolution of the Vitruvian Recipes over 500 years of floor-making techniques: The case studies of the Domus delle Bestie Ferite and the Domus di Tito Macro (Aquileia, Italy)
.
Archaeometry
 ,
60
,
185
206
.
Sengupta
,
R.
(
1971
)
Influence of certain Harappan architectural features on some texts of early-historic period
.
The Indian Journal of History of Science
 ,
6
,
23
26
.
Shahack-Gross
,
R.
,
Albert
,
R.M.
,
Gilboa
,
A.
,
Nagar-Hilman
,
O.
,
Sharon
,
I.
and
Weiner
,
S.
(
2005
)
Geoarchaeology in an urban context: the uses of space in a Phoenician monumental building at Tel Dor (Israel)
.
Journal of Archaeological Science
 ,
32
,
1417
1431
.
Sharma
,
D.P.
and
Sharma
,
M.
(
2003
)
Panorama of Harappan civilization
 .
New Delhi
.
Shaw
,
J.
(
1973
)
Minoan Architecture, Materials and Techniques
 .
Annuario, NS XXXIII
,
Roma
.
Shi
,
C.
,
Roy
,
D.
and
Krivenko
,
P.
(
2006
)
Alkali-activated Cements and Concretes
 .
CRC Press
,
Boca Raton, Florida, USA
.
Shi
,
C.
,
Jiménez
,
A.F.
and
Palomo
,
A.
(
2011
)
New cements for the 21st century: the pursuit of an alternative to Portland cement
.
Cement and Concrete Research
 ,
41
,
750
763
.
Sickels
L.-B.
(
1981
)
Organic additives in mortars
.
Edinburgh Architecture Research
 ,
8
.
7
20
.
Siddall
,
R.
(
2000
)
The use of volcaniclastic material in Roman hydraulic concretes: A brief review
. Pp.
339
344
in:
Archaeology of Geological Catastrophes
  (
W.J.
McGuire
,
D.R.
Griffiths
,
P.L.
Hancock
and
I.S.
Stewart
, editors).
Special Publication, 171, The Geological Society
,
London
.
Siddall
,
R.
(
2011
)
From kitchen to bathhouse: the use of waste ceramics as pozzolanic additives in Roman mortars
. Pp.
152
168
in:
Building Roma Aeterna
 
(Å.
Ringbom
and
R.L.
Hohlfelder
, editors). (
Proceedings) The Finnish Society of Sciences and Letters
,
Helsinki
.
Singh
,
M.
(
1993
)
Analysis and characterization of Charminar lime plaster
.
Current Science-Bangalore
 ,
64
,
760
764
.
Singh
,
M.
,
Jain
,
K.K.
and
Singh
,
T.
(
1990
)
Some studies on the suitability of lime mortars based on ancient Indian formulations for restoration purposes
. Pp.
151
158
in:
Superfici dell’architettura: le finiture
  (
G.
Biscontin
and
S.
Volpin
, editors).
Atti del convegno di studi
,
Bressanone
, 26–29 June 1990.
Libreria Progetto Editore
,
Italy
.
Singh
,
M.
,
Waghmare
,
S.
and
Kumar
,
S.V.
(
2014
)
Characterization of lime plasters used in 16th century Mughal monument
.
Journal of Archaeological Science
 ,
42
,
430
434
.
Singh
,
M.
,
Kumar
,
S.V.
and
Waghmare
,
S.A.
(
2015
)
Characterization of 6–11th century AD decorative lime plasters of rock cut caves of Ellora
.
Construction and Building Materials
 ,
98
,
156
170
.
Snellings
,
R.
(
2016
)
X-ray powder diffraction applied to cement
. Pp.
107
176
in:
A Practical Guide to Microstructural Analysis of Cementitious Materials
  (
K.
Scrivener
,
R.
Snellings
and
B.
Lothenbach
, editors).
CRC Press
,
Boca Raton, Florida, USA
.
Snellings
,
R.
,
Mertens
,
G.
,
Cizer
,
Ö.
and
Elsen
,
J.
(
2010
)
Early age hydration and pozzolanic reaction in natural zeolite blended cements: Reaction kinetics and products by in situ synchrotron X-ray powder diffraction
.
Cement and Concrete Research
 ,
40
,
1704
1713
.
Snellings
,
R.
,
Mertens
,
G.
and
Elsen
,
J.
(
2012
)
Supplementary cementitious materials
. Pp.
211
278
in:
Applied Mineralogy of Cement & Concrete
 
(M.A.T.M.
Broekmans
and
H.
Pöllmann
, editors).
Reviews in Mineralogy and Geochemistry, 74, Mineralogical Society of America and Geochemical Society
,
Chantilly, Virginia, USA
.
Sokol
,
E.V.
,
Novikov
,
I.S.
,
Vapnik
,
Y.
and
Sharygin
,
V.V.
(
2007
)
Gas fire from mud volcanoes as a trigger for the appearance of high-temperature pyrometamorphic rocks of the Hatrurim Formation (Dead Sea area)
.
In Doklady Earth Sciences
  (Vol.
413
, No.
2
, pp.
474
480
). Nauka/Interperiodica.
Song
,
Y.X.
and
KaiWu
,
T.G.
(
1982
)
The exploitation of the works of Nature
 . First written in 1587.
Times and Culture Publishing Co.,
Taibei, China
.
Srejović
,
D.
(
1972
)
Europe’s First Monumental Sculpture: New Discoveries at Lepenski Vir
 .
Thames & Hudson
,
London
.
Srejović
,
D.
(
1981
)
Lepenski Vir: Menschenbilder einer frühen europäischen Kultur
 .
Verlag Philipp von Zabern
,
Mainz am Rhein, Germany.
Staubach
,
S.
(
2013
)
Clay: The History and Evolution of Humankind’s Relationship with Earth’s Most Primal Element
 .
Penguin Group
,
New York
.
Stoops
,
G.
,
Canti
,
M.G.
and
Kapur
,
S.
(
2017
)
Calcareous mortars, plasters, and floors
. Pp.
189
199
in:
Archaeological Soil and Sediment Micromorphology
  (
C.
Nicosia
and
G.
Stoops
, editors).
Wiley Blackwell
,
Hoboken, New Jersey, USA
.
Sui Pheng
,
L.
(
2001
)
Construction of dwellings and structures in ancient China
.
Structural Survey
 ,
19
,
262
274
.
Sullivan
,
S.
and
Mackay
,
R.
(editors) (
2012
)
Archaeological sites: conservation and management
 . Vol.
5
.
Getty Publications
,
Los Angeles, California, USA
.
Taylor
,
H.F.
(
1997
)
Cement Chemistry
 .
Thomas Telford
,
London
.
Theodoridou
,
M.
,
Ioannou
,
I.
and
Philokyprou
,
M.
(
2013
)
New evidence of early use of artificial pozzolanic material in mortars
.
Journal of Archaeological Science
 ,
40
,
3263
3269
.
Thickett
,
D.
,
Odlyha
,
M.
and
Ling
,
D.
(
2002
)
An improved firing treatment for cuneiform tablets
.
Studies in Conservation
 ,
47
,
1
11
.
Thirumalini
,
S.
,
Ravi
,
R.
,
Sekar
,
S.K.
and
Nambirajan
,
M.
(
2015
)
Knowing from the past – Ingredients and technology of ancient mortar used in Vadakumnathan temple, Tirussur, Kerala, India
.
Journal of Building Engineering
 ,
4
,
101
112
.
Thomas
,
J.J.
,
Biernacki
,
J.J.
,
Bullard
,
J.W.
,
Bishnoi
,
S.
,
Dolado
,
J.S.
,
Scherer
,
G.W.
and
Luttge
,
A.
(
2011
)
Modeling and simulation of cement hydration kinetics and microstructure development
.
Cement and Concrete Research
 ,
41
,
1257
1278
.
Thuesen
,
I.
and
Gwozdz
,
R.
(
1982
)
Lime plaster in Neolithic Hama, Syria. A preliminary report
.
Paléorient
 ,
8
,
99
103
.
Valentini
,
L.
(
2013
)
RieCalc: Quantitative phase analysis of hydrating cement pastes
.
Journal of Applied Crystallography
 ,
46
,
1899
1902
.
Valentini
,
L.
,
Dalconi
,
M.C.
,
Favero
,
M.
,
Artioli
,
G.
and
Ferrari
,
G.
(
2015
)
In situ XRD measurement and quantitative analysis of hydrating cement: Implications for sulfate incorporation in C–S–H
.
Journal of the American Ceramic Society
 ,
98
,
1259
1264
.
Van Balen
,
K.
(
2005
)
Carbonation reaction of lime, kinetics at ambient temperature
.
Cement and Concrete Research
 ,
35
,
647
657
.
Van Balen
,
K.
,
Papayianni
,
I.
,
Van Hees
,
R.
,
Binda
,
L.
and
Waldum
,
A.
(
2005
)
Introduction to requirements for and functions and properties of repair mortars
.
Materials and Structures
 ,
38
,
781
785
.
van Strydonck
,
M.J.
,
Dupas
,
M.
and
Keppens
,
E.
(
1989
)
Isotopic fractionation of oxygen and carbon in lime mortar under natural environmental conditions
.
Radiocarbon
 ,
31
,
610
618
.
Vandiver
,
P.B.
,
Soffer
,
O.
,
Klima
,
B.
and
Svoboda
,
J.
(
1989
)
Origins of ceramic technology at Dolní Veštonice, Czechoslovakia
.
Science
 ,
246
,
1002
1008
.
Vatandoust
,
R.
,
Dehkordi
,
M.H.
,
Abdollahi
,
P.
and
Madani
,
F.S.
(
2011
)
Development of Earthen Architecture in Iran
. Pp.
27
39
in:
TerrAsia 2011
  (
H.
Wang
,
S.
Kim
,
H.
Guillaud
and
D.
Gandreau
, editors).
Proceedings of the 2011 International Conference on Earthen Architecture in Asia
,
Mokpo, Terrakorea.
Vicat
,
L.J.
(
1818
)
Recherches expérimentales sur les chaux de construction, les bétons et les mortiers ordinaires
 .
Goujon, Paris
.
Vicat
,
L.J.
(
1828
)
Mortier et Ciment calcaires
 .
Paris
.
Villaseor Alonso
,
M.I.
(
2009
)
Lowland Maya lime plaster technology: A diachronic approach
. Ph.D. Dissertation.
University College London.
Villaseor
,
I.
and
Price
,
C.A.
(
2008
)
Technology and decay of magnesian lime plasters: the sculptures of the funerary crypt of Palenque, Mexico
.
Journal of Archaeological Science
 ,
35
,
1030
1039
.
Voltolini
,
M.
,
Dalconi
,
M.C.
,
Artioli
,
G.
,
Parisatto
,
M.
,
Valentini
,
L.
,
Russo
,
V.
,
Bonnin
,
A.
and
Tucoulou
,
R.
(
2013
)
Understanding cement hydration at the microscale: new opportunities from pencil-beam synchrotron X-ray diffraction tomography
.
Journal of Applied Crystallography
 ,
46
,
142
152
.
Walker
,
C.B.F.
(
1987
)
Cuneiform
 .
University of California Press
,
Los Angeles, California, USA
.
Weber
,
J.
,
Bayer
,
K.
and
Pintér
,
F.
(
2012
)
Nineteenth century “Novel” building materials: Examples of various historic mortars under the microscope
. Pp.
89
103
in:
Historic Mortars
 .
Springer
,
Dordrecht, The Netherlands
.
Weil
,
M.
,
Dombrowski
,
K.
and
Buchwald
,
A.
(
2009
)
Life-cycle analysis of geopolymers
. Pp.
194
210
in:
Geopolymers: Structures, Processing, Properties and Industrial Applications
  (
J.L.
Provis
and
J.S.J.
Van Deventer
, editors).
Elsevier
.
Wernecke
,
D.C.
(
2008
)
A burning question: Maya lime technology and the Maya forest
.
Journal of Ethnobiology
 ,
28
,
200
210
.
Williams
,
R.
(
2004
)
Lime Kilns and Lime Burning
 .
Osprey Publishing
,
Oxford, UK
.
Worrell
,
E.
,
Price
,
L.
,
Martin
,
N.
,
Hendriks
,
C.
and
Meida
,
L.O.
(
2001
)
Carbon dioxide emissions from the global cement industry
.
Annual Review of Energy and the Environment
 ,
26
,
303
329
.
Wright
,
G.R.H.
(
1983
)
Puddled mud walling: An ancient survival in the Orient
.
Mitteilungen der Deutschen Orientgesellschaft zu Berlin Berlin
 ,
115
,
9
14
.
Wright
,
G.R.H.
(
2005
)
Ancient Building Technology
, Volume
2
:
Materials (2 Vols). Brill
,
Leiden, The Netherlands
.
Wu
,
X.
,
Zhang
,
C.
,
Goldberg
,
P.
,
Cohen
,
D.
,
Pan
,
Y.
,
Arpin
,
T.
and
Bar-Yosef
,
O.
(
2012
)
Early pottery at 20,000 years ago in Xianrendong Cave, China
.
Science
 ,
336
,
1696
1700
.
Yang
,
F.
,
Zhang
,
B.
,
Pan
,
C.
and
Zeng
,
Y.
(
2009
)
Traditional mortar represented by sticky rice lime mortar – One of the great inventions in ancient China
.
Science in China Series E: Technological Sciences
 ,
52
,
1641
1647
.
Yu
,
H.Y.
and
Chen
,
D.
(
2004
)
Protection and development of Qiantan River’s dyke constructed in Ming and Qing dynasty as a tourism resource
.
Zhejiang Hydrotechnology
 ,
134
,
9
10
.
Zendri
,
E.
,
Lucchini
,
V.
,
Biscontin
,
G.
and
Morabito
,
Z.M.
(
2004
)
Interaction between clay and lime in “cocciopesto” mortars: a study by 29Si MAS spectroscopy
.
Applied Clay Science
 ,
25
,
1
7
.
Zeng
,
Y.Y.
,
Zhang
,
B.J.
and
Liang
,
X.
(
2008
)
A case study and mechanism investigation of typical mortars used on ancient architecture in China
.
Thermochimica Acta
 ,
473
,
1
6
.
Zhang
,
K.
,
Zhang
,
H.
,
Fang
,
S.
,
Li
,
J.
,
Zheng
,
Y.
and
Zhang
,
B.
(
2014
)
Textual and experimental studies on the compositions of traditional Chinese organic–inorganic mortars
.
Archaeometry
 ,
56
(
S1
),
100
115
.
Zhao
,
P.
,
Jackson
,
M.D.
,
Zhang
,
Y.
,
Li
,
G.
,
Monteiro
,
P.J.
and
Yang
,
L.
(
2015
)
Material characteristics of ancient Chinese lime binder and experimental reproductions with organic admixtures
.
Construction and Building Materials
 ,
84
,
477
488
.
Zoppi
,
A.
,
Lofrumento
,
C.
,
Ricci
,
M.
,
Cantisani
,
E.
,
Fratini
,
T.
and
Castellucci
,
E.M.
(
2012
)
A novel piece of Minoan art in Italy: the first spectroscopic study of the wall paintings from Phaistos
.
Journal of Raman Spectroscopy
 ,
43
,
1663
1670
.

Figures & Tables

Figure 1.

The massive body of the Deffufa (‘mud-brick building’ in Nubian) of Kerma, Nubia. It was built entirely of sun-dried bricks and was the reference structure of the classic Kush civilization (2000–1500 BC).

Figure 1.

The massive body of the Deffufa (‘mud-brick building’ in Nubian) of Kerma, Nubia. It was built entirely of sun-dried bricks and was the reference structure of the classic Kush civilization (2000–1500 BC).

Figure 2.

Mud-brick qubba in the cemetery from the Islamic period near Dongola, Sudan. Qubbas are domed mausoleums which contain the grave of a saint or some important personage.

Figure 2.

Mud-brick qubba in the cemetery from the Islamic period near Dongola, Sudan. Qubbas are domed mausoleums which contain the grave of a saint or some important personage.

Figure 3.

Sun-dried mud bricks with clay mortar in a Neolithic wall at Çatalhöyük, Turkey.

Figure 3.

Sun-dried mud bricks with clay mortar in a Neolithic wall at Çatalhöyük, Turkey.

Figure 4.

An internal wall of a living quarter in Çatalhöyük showing wall plastering and decorations.

Figure 4.

An internal wall of a living quarter in Çatalhöyük showing wall plastering and decorations.

Figure 5.

Modern production of sun-dried bricks in Sudan.

Figure 5.

Modern production of sun-dried bricks in Sudan.

Figure 6.

Mud-brick walls in Sardinian houses. Traditional earthen architecture is preserved alongside to modern concrete building.

Figure 6.

Mud-brick walls in Sardinian houses. Traditional earthen architecture is preserved alongside to modern concrete building.

Figure. 7.

Inscribed bricks in the wall of Chogha Zanbil, the great Elamite zigurrath in Iran, some 30 km south-east of Susa.

Figure. 7.

Inscribed bricks in the wall of Chogha Zanbil, the great Elamite zigurrath in Iran, some 30 km south-east of Susa.

Figure 8.

Optical micrograph of the thin section of a Medieval lime mortar from the Sachuidic castle, Friuli, Italy. The images in plane polarized light (a) and cross polarized light (b) show fragments of geological carbonate, lime lumps and the lime binder matrix.

Figure 8.

Optical micrograph of the thin section of a Medieval lime mortar from the Sachuidic castle, Friuli, Italy. The images in plane polarized light (a) and cross polarized light (b) show fragments of geological carbonate, lime lumps and the lime binder matrix.

Figure 9.

Cathodoluminescence image of a mortar showing sub-mm grains of geological carbonate embedded in the mortar binder.

Figure 9.

Cathodoluminescence image of a mortar showing sub-mm grains of geological carbonate embedded in the mortar binder.

Figure 10.

The partially reconstructed Throne Room of King Minos in Knossos, Crete showing the ample use of lime plaster for wall decorations.

Figure 10.

The partially reconstructed Throne Room of King Minos in Knossos, Crete showing the ample use of lime plaster for wall decorations.

Figure 11.

The Great Stupa at Sanchi (3rd century BC) is the oldest stone building in India and one of the largest fired-brick domes (photo by Nagarjun Kandukuru, CC-BY-SA-2.0).

Figure 11.

The Great Stupa at Sanchi (3rd century BC) is the oldest stone building in India and one of the largest fired-brick domes (photo by Nagarjun Kandukuru, CC-BY-SA-2.0).

Figure 12.

The Ellora caves show a spectacular labyrinth of rock carvings and paintings. Much of the artwork is plastered with one of the earliest examples of kemp-loaded lime of the 6th century AD.

Figure 12.

The Ellora caves show a spectacular labyrinth of rock carvings and paintings. Much of the artwork is plastered with one of the earliest examples of kemp-loaded lime of the 6th century AD.

Figure 13.

Reaction rim formed around a volcanic fragment in a lime matrix. The rim provides direct evidence of the pozzolanic reaction between the lime binder and the Si, Al-rich glass fragments inserted in the mix.

Figure 13.

Reaction rim formed around a volcanic fragment in a lime matrix. The rim provides direct evidence of the pozzolanic reaction between the lime binder and the Si, Al-rich glass fragments inserted in the mix.

Figure 14.

Simplified lime-silica-alumina diagram showing the clinker phases and some of the phases formed during cement hydration and pozzolanic reactions. Modified from Lothenbach et al. (2011).

Figure 14.

Simplified lime-silica-alumina diagram showing the clinker phases and some of the phases formed during cement hydration and pozzolanic reactions. Modified from Lothenbach et al. (2011).

Figure 15.

(a) Prismatic crystals of ettringite growing amidst C-S-H felt during the hydration of a Portland cement, and (b) well developed platy crystals of Portlandite. Images obtained by ESEM. (Courtesy of D. Salvioni, Mapei S.p.a.).

Figure 15.

(a) Prismatic crystals of ettringite growing amidst C-S-H felt during the hydration of a Portland cement, and (b) well developed platy crystals of Portlandite. Images obtained by ESEM. (Courtesy of D. Salvioni, Mapei S.p.a.).

Figure 16.

Reinforced concrete structures by Charles-Édouard Jeanneret (Le Corbusier): (a) The convent of Sainte Marie de La Tourette, France (1953–1960) (photo by Alexandre Norman, French Wikipedia, CC-BY-SA-3.0); (b) The palace of Assembly, Chandigarh, India (1952–1961) (photo by English Wikipedia, CC-BY-SA-2.0).

Figure 16.

Reinforced concrete structures by Charles-Édouard Jeanneret (Le Corbusier): (a) The convent of Sainte Marie de La Tourette, France (1953–1960) (photo by Alexandre Norman, French Wikipedia, CC-BY-SA-3.0); (b) The palace of Assembly, Chandigarh, India (1952–1961) (photo by English Wikipedia, CC-BY-SA-2.0).

Figure 17.

Time resolved XRPD patterns of a cement paste during the hydration process.

Figure 17.

Time resolved XRPD patterns of a cement paste during the hydration process.

Figure 18.

Virtual modelling of the microstructural evolution of cement can be compared directly to the experimental results obtained by computed micro-tomography (μ-CT).

Figure 18.

Virtual modelling of the microstructural evolution of cement can be compared directly to the experimental results obtained by computed micro-tomography (μ-CT).

Figure 19.

Young’s Modulus vs. embodied energy per unit volume. (Chart created using CES EduPack, 2017, Granta Design Ltd. http://teachingresources.grantadesign.com/Charts-overview).

Figure 19.

Young’s Modulus vs. embodied energy per unit volume. (Chart created using CES EduPack, 2017, Granta Design Ltd. http://teachingresources.grantadesign.com/Charts-overview).

Figure 20.

Brick masonry of an old factory converted to a modern building. The OPC cement used to repoint the joints is deleterious in terms of rigidity and salt leaching.

Figure 20.

Brick masonry of an old factory converted to a modern building. The OPC cement used to repoint the joints is deleterious in terms of rigidity and salt leaching.

Table 1.

Main types of inorganic binders, their nature and reaction processes.

Type of binderStarting materialAppx. T of firing (°C)Reactive material productReaction process
Binders based on carbonateLime plasterlimestone800–1000Quicklime (CaO) Slaked lime (Ca(OH)2)aerial carbonation
Hydraulic Lime plasterlimestoneSlaked lime + pozzolanpozzolanic reaction
Natural Hydraulic Lime plasterlimestone + clays/volcanic glassNatural hydraulic limehydration reaction
Magnesian plasterdolomiteSlaked magnesia-lime (Ca(OH)2) (Mg(OH)2)aerial carbonation
Binders based on gypsumGypsum plaster (Plaster of Paris)gypsum250–300Bassanite CaSO4·0.5H2Ohydration
Binders based on Portland clinkerPortland clinker (cement)limestone + clays/marls1400–1450Clinker phases (alite C3S, belite C2S, Ca-aluminate C3A)cement hydration
Type of binderStarting materialAppx. T of firing (°C)Reactive material productReaction process
Binders based on carbonateLime plasterlimestone800–1000Quicklime (CaO) Slaked lime (Ca(OH)2)aerial carbonation
Hydraulic Lime plasterlimestoneSlaked lime + pozzolanpozzolanic reaction
Natural Hydraulic Lime plasterlimestone + clays/volcanic glassNatural hydraulic limehydration reaction
Magnesian plasterdolomiteSlaked magnesia-lime (Ca(OH)2) (Mg(OH)2)aerial carbonation
Binders based on gypsumGypsum plaster (Plaster of Paris)gypsum250–300Bassanite CaSO4·0.5H2Ohydration
Binders based on Portland clinkerPortland clinker (cement)limestone + clays/marls1400–1450Clinker phases (alite C3S, belite C2S, Ca-aluminate C3A)cement hydration
Table 2.

Main phase components of ordinary Portland clinkers.

Common phase nameMineral nameCompositionCement notationAppx. wt %
Alite (tricalcium silicate)hatruriteCa3SiO5C3S50–70
Belite (dicalcium silicate)larniteCa2SiO4C2S15–30
Aluminate (tricalcium aluminate)Ca3Al2O6C3A5–10
Ferrite (tetracalcium aluminoferrite)brownmilleriteCa2(Al, Fe)2O5C4AF5–15
Common phase nameMineral nameCompositionCement notationAppx. wt %
Alite (tricalcium silicate)hatruriteCa3SiO5C3S50–70
Belite (dicalcium silicate)larniteCa2SiO4C2S15–30
Aluminate (tricalcium aluminate)Ca3Al2O6C3A5–10
Ferrite (tetracalcium aluminoferrite)brownmilleriteCa2(Al, Fe)2O5C4AF5–15

Contents

GeoRef

References

References

Abrams
,
E.M.
and
Freter
,
A.
(
1996
)
A Late Classic lime-plaster kiln from the Maya centre of Copan, Honduras
.
Antiquity
 ,
70
,
422
428
.
Adam
,
J.P.
(
2005
)
Roman Building: Materials and Techniques
 .
Routledge
,
London
.
Addis
,
A.
,
Secco
,
M.
,
Preto
,
N.
,
Marzaioli
,
F.
,
Passariello
,
I.
,
Brogiolo
,
G.P.
,
Chavarria Arnau
,
A.
,
Artioli
,
G.
and
Terrasi
,
F.
(
2016
)
New strategies for radiocarbon dating of mortars: Multi-step purification of the lime binder
. Pp.
665
672
in:
Proceedings of the 4th Historic Mortars Conference – HMC 2016
(
I.
Papayianni
M.
Stefanidou
and
V.
Pachta
, editors).
Aristotle University of Thessaloniki
,
Greece
.
Affonso
,
M.T.C.
and
Freiberg
,
E.P.
(
2001
)
Neolithic lime plasters and pozzolanic reactions. Are they occasional occurrences?
Pp.
9
13
in:
Lux Orientis. Archaeologie zwishen Asien and Europa
  (
R.M.
Boehmer
and
J.
Maran
, editors).
Festschrift fur Havald Hauptmann zum 65 Geburstag. Verlag Marie Leidorf GmbH.
Rahden/Westfalia, Germany.
Agnew
,
N.
and
Bridgland
,
J.
(editors) (
2006
)
Of the Past, for the Future: Integrating Archaeology and Conservation
 .
Proceedings of the Conservation Theme at the 5th World Archaeological Congress
,
Washington, DC
, 22–26 June 2003.
Getty Publications
,
Los Angeles, California, USA
.
Alexander
,
W.R.
and
Blaser
,
P.C.
(editors) (
2002
)
The use of technical natural analogues in radioactive waste disposal
 .
Nagra Unpublished Project Report,
Nagra, Wettingen, Switzerland
.
Alexander
,
W.R.
and
Smellie
,
J.A.T.
(
1998
)
Maqarin natural analogue project: synthesis report on Phases I, II and III
 .
Nagra Unpublished Project Report,
Nagra, Wettingen, Switzerland
.
Al-Rawas
,
A.A.
,
Hago
,
A.W.
,
Corcoran
,
T.C.
and
Al-Ghafri
,
K.M.
(
1998
)
Properties of Omani artificial pozzolana (sarooj)
.
Applied Clay Science
 ,
13
,
275
292
.
Al-Rawas
,
A.A.
,
Hago
,
A.W.
,
Al-Lawati
,
D.
and
Al-Battashi
,
A.
(
2001
)
The Omani artificial pozzolans (sarooj)
.
Cement, Concrete and Aggregates
 ,
23
,
19
26
.
Alvarez
,
J.I.
,
Navarro
,
I.
,
Martın
,
A.
and
Casado
,
P.G.
(
2000
)
A study of the ancient mortars in the north tower of Pamplona’s San Cernin church
.
Cement and Concrete Research
 ,
30
,
1413
1419
.
Ambers
,
J.
(
1987
)
Stable carbon isotope ratios and their relevance to the determination of accurate radiocarbon dates for lime mortars
.
Journal of Archaeological Science
 ,
14
,
569
576
.
Aranda
,
M.A.
(
2016
)
Recent studies of cements and concretes by synchrotron radiation crystallographic and cognate methods
.
Crystallography Reviews
 ,
22
,
150
196
.
Arandigoyen
,
M.
,
Bicer-Simsir
,
B.
,
Alvarez
,
J.I.
and
Lange
,
D.A.
(
2006
)
Variation of microstructure with carbonation in lime and blended pastes
.
Applied Surface Science
 .
252
,
7562
7571
.
Arkun
,
B.H.
(
2003
)
Neolithic plasters in the Near East: Çatalhöyük Building 5, a case study
. Master’s Thesis,
University of Pennsylvania
.
Artioli
,
G.
(
2010
)
Scientific Methods and Cultural Heritage: An Introduction to the Application of Materials Science to Archaeometry and Conservation Science
 .
Oxford University Press
.
Artioli
,
G.
and
Secco
,
M.
(
2016
)
Modern and ancient masonry: Nature and role of the binder
. Pp.
3
10
in:
Brick and Block Masonry – Trends, Innovations and Challenges
  (
C.
Modena
,
F.
Da Porto
and
M.R.
Valluzzi
, editors).
Proceedings of the 16th International Brick and Block Masonry Conference
,
Padova
, 26-30 June 2016.
Taylor & Francis Group
,
London
.
Artioli
,
G.
,
Nicola
,
C.
,
Montana
,
G.
,
Angelini
,
I.
,
Nodari
,
L.
and
Russo
,
U.
(
2009
)
The blue enamels in the baroque decorations of the churches of Palermo, Sicily: Fe2+-coloured glasses from lime kilns
.
Archaeometry
 ,
51
,
197
213
.
Artioli
,
G.
,
Cerulli
,
T.
,
Cruciani
,
G.
,
Dalconi
,
M.C.
,
Ferrari
,
G.
,
Parisatto
,
M.
,
Rack
,
A.
and
Tucoulou
,
R.
(
2010
)
X-ray diffraction microtomography (XRD-CT), a novel tool for non-invasive mapping of phase development in cement materials
.
Analytical and ioanalytical Chemistry
 ,
397
,
2131
2136
.
Artioli
,
G.
,
Valentini
,
L.
,
Dalconi
,
M.C.
,
Parisatto
,
M.
,
Voltolini
,
M.
,
Russo
,
V.
and
Ferrari
,
G.
(
2014a
)
Imaging of nano-seeded nucleation in cement pastes by X-ray diffraction tomography
.
International Journal of Materials Research
 ,
105
,
628
631
.
Artioli
,
G.
,
Valentini
,
L.
,
Voltolini
,
M.
,
Dalconi
,
M.C.
,
Ferrari
,
G.
and
Russo
,
V.
(
2014b
)
Direct imaging of nucleation mechanisms by synchrotron diffraction micro-tomography: superplasticizer-induced change of C–S–H nucleation in cement
.
Crystal Growth & Design
 ,
15
,
20
23
.
Ashby
,
M.F.
(
2013
)
Materials and the Environment: Eco-informed Material Choice
 .
Elsevier, Amsterdam and Butterworth-Heinemann,
Oxford.
Avrami
,
E.
,
Guillaud
,
H.
and
Hardy
M.
(editors) (
2008
)
Terra Literature Review. An Overview of Research in Earthen Architecture Conservation
 .
The Getty Conservation Institute
,
Los Angeles
.
Aygen
,
Z.
(
2013
)
International Heritage and Historic Building Conservation: Saving the World’s Past
  (Vol.
3)
.
Routledge
,
London
.
Barba
,
L.
,
Blancas
,
J.
,
Manzanilla
,
L.R.
,
Ortiz
,
A.
,
Barca
,
D.
,
Crisci
,
G.M.
,
Miriello
,
D.
and
Pecci
,
A.
(
2009
)
Provenance of the limestone used in Teotihuacan (Mexico): A methodological approach
.
Archaeometry
 ,
51
,
525
545
.
Barcelo
,
L.
,
Kline
,
J.
,
Walenta
,
G.
and
Gartner
,
E.
(
2014
)
Cement and carbon emissions
.
Materials and Structures
 ,
47
,
1055
1065
.
Baronio
,
G.
and
Binda
,
L.
(
1997
)
Study of the pozzolanicity of some bricks and clays
.
Construction and Building Materials
 ,
11
,
41
46
.
Bakolas
,
A.
,
Aggelakopoulou
,
E.
and
Moropoulou
,
A.
(
2008
)
Evaluation of pozzolanic activity and physico-mechanical characteristics in ceramic powder-lime pastes
.
Journal of Thermal Analysis and Calorimetry
 ,
92
,
345
351
.
Barnes
,
P.
and
Bensted
,
J.
(
2002
)
Structure and Performance of Cements
 .
CRC Press
,
Boca Raton, Florida, USA
.
Bar-Yosef
,
O.
(
1986
)
The walls of Jericho: An alternative interpretation
.
Current Anthropology
 ,
27
,
157
162
.
Bailey
,
S.W.
(
1988
)
Hydrous Phyllosilicates (Exclusive of Micas)
(
S.W.
Bailey
, editor).
Reviews in Mineralogy
 ,
19
.
Mineralogical Society of America
.
Chantilly, Virginia, USA
.
Bellotto
,
M.
and
Signes-Frehel
,
M.
(
1998
)
The Role of Powder X-ray Diffraction in the Cement Industry
.
European Powder Diffraction Conference
.
Materials Science Forum
 ,
Vols
.
278
281
.
Bellotto
,
M.
,
Gualtieri
,
A.
,
Artioli
,
G.
and
Clark
,
S.M.
(
1995
)
Kinetic study of the kaolinite-mullite reaction sequence. Part I: kaolinite dehydroxylation
.
Physics and Chemistry of Minerals
 ,
22
,
207
217
.
Bensted
,
J.
(
1999
)
A discussion of the paper “Use of cactus in mortars and concrete” by S. Chandra, L. Eklund, and R.R. Villarreal. – Authors’reply
.
Cement and Concrete Research
 ,
29
,
967
969
.
Bentur
,
A.
(
2002
)
Cementitious materials – Nine millennia and a new century: Past, present, and future. American Society of Civil Engineers, 150th Anniversary Paper
.
Journal of Materials in Civil Engineering
 , JAN/FEB
2002
,
2
22
.
Bequette
,
A.
and
Dhanjal
,
S.
(
2011
)
Continuous X-ray diffraction at the Buzzi Unicem festus plant
. Pp.
1
10
in:
Cement Industry Technical Conference, 2011 IEEE-IAS/PCA 53rd.
IEEE
.
Biton
,
R.
,
Goren
,
Y.
and
Goring-Morris
,
A.N.
(
2014
)
Ceramics in the Levantine Pre-Pottery Neolithic B: evidence from Kfar HaHoresh, Israel
.
Journal of Archaeological Science
 ,
41
,
740
748
.
Blauer-Bohm
,
C.
and
Jagers
,
E.
(
1997
)
Analysis and recognition of dolomitic lime mortars
. Pp.
223
235
in:
Roman Wall Painting: Materials, Techniques, Analysis and Conservation
  (
H.
Bearat
,
M.
Fuchs
,
M.
Maggetti
and
D.
Paunier
, editors).
Proceedings of the International Workshop
,
Fribourg
, 7–9 March 1996.
Institute of Mineralogy and Petrography
,
Fribourg, Germany
.
Blezard
,
R.G.
(
2003
)
The history of calcareous cements
. Pp.
1
19
in:
Lea’s Chemistry of Cement and Concrete
  (
P.C.
Hewlett
, editor).
Butterworth-Heinemann
,
Oxford, UK
.
Böke
,
H.
,
Akkurt
,
S.
,
İpekoğlu
,
B.
and
Uğurlu
,
E.
(
2006
)
Characteristics of brick used as aggregate in historic brick-lime mortars and plasters
.
Cement and Concrete Research
 ,
36
,
1115
1122
.
Bonetto
,
J.
,
Artioli
,
G.
,
Secco
,
M.
and
Addis
,
A.
(
2016
)
The use of the pozzolanic ashes in the big yards of Cisalpine Gaul during the Roman Republican Age: The cases of Aquileia and Ravenna
. Pp.
29
44
in:
Proceedings of the 5th International Workshop on the Archaeology of Roman Construction
(
S.
Camporeale
,
J.
DeLaine
and
A.
Pizzo
, editors).
Oxford
, 11-12 April 2015.
“Arqueología de la Construcción V. Manmade materials, engineering and infrastructure”
 .
CSIC
,
Madrid
.
Bonsall
,
C.
,
Radovanović
,
I.
,
Roksandic
,
M.
,
Cook
,
G.T.
,
Higham
,
T.
and
Pickard
,
C.
(
2008
)
Dating burial practices and architecture at Lepenski Vir
. Pp.
175
204
in:
The Iron Gates in Prehistory: New Perspectives
  (
C.
Bonsall
,
I.
Radovanović
: and
V.
Boroneanţ
, editors).
Archaeopress
,
Oxford, UK
.
Borić
,
D.
(
2002
)
The Lepenski Vir conundrum: reinterpretation of the Mesolithic and Neolithic sequences in the Danube Gorges
.
Antiquity
 ,
76
,
1026
1039
.
Brandon
,
C.
,
Hohlfelder
,
R.L.
,
Oleson
,
J.P.
and
Stern
,
C.
(
2005
)
The Roman Maritime Concrete Study (ROMACONS): the harbour of Chersonisos in Crete and its Italian connection
.
Méditerranée. Revue géographique des pays méditerranéens/Journal of Mediterranean Geography
 ,
104
,
25
29
.
Brandon
,
C.J.
,
Hohlfelder
,
R.L.
,
Jackson
,
M.D.
and
Oleson
,
J.P.
(
2014
)
Building for eternity: the history and technology of Roman concrete engineering in the sea
 .
Oxbow Books
.
Bras
,
A.
and
Henriques
,
F.M.
(
2012
)
Natural hydraulic lime based grouts–The selection of grout injection parameters for masonry consolidation
.
Construction and Building Materials
 ,
26
,
135
144
.
Brown
,
G.
and
Brindley
,
G.W.
(editors) (
1980
)
Crystal Structures of Clay Minerals and their X-ray Identification
 .
Monograph 5. Mineralogical Society of Great Britain & Ireland,
London.
Bullard
,
J.W.
,
Jennings
,
H.M.
,
Livingston
,
R.A.
,
Nonat
,
A.
,
Scherer
,
G.W.
,
Schweitzer
,
J.S.
,
Scrivener
,
K.L.
and
Thomas
,
J.J.
(
2011
)
Mechanisms of cement hydration
.
Cement and Concrete Research
 ,
41
,
1208
1223
.
Burg
,
A.
,
Starinsky
,
A.
,
Bartov
,
Y.
and
Kolodny
,
Y.
(
1991
)
Geology of the Hatrurim formation (“mottled zone”) in the Hatrurim basin
.
Israel Journal of Earth Sciences
 ,
40
,
107
124
.
Buyle
,
M.
,
Braet
,
J.
and
Audenaert
,
A.
(
2013
)
Life cycle assessment in the construction sector: A review
.
Renewable and Sustainable Energy Reviews
 ,
26
,
379
388
.
Callebaut
,
K.
,
Elsen
,
J.
,
Van Balen
,
K.
and
Viaene
,
W.
(
2000
)
Historical and scientific study of hydraulic mortars from the 19th century
. Pp.
125
132
in:
Proceedings of the International RILEM-workshop “Historic Mortars: Characteristics and Tests”
,
Paisley, UK
.
Callebaut
,
K.
,
Elsen
,
J.
,
Van Balen
,
K.
and
Viaene
,
W.
(
2001
)
Nineteenth century hydraulic restoration mortars in the Saint Michael’s Church (Leuven, Belgium): Natural hydraulic lime or cement?
Cement and Concrete Research
 ,
31
,
397
403
.
Cameron
,
M.A.S.
,
Jones
,
R.E.
and
Philippakis
,
S.E.
(
1977
)
Scientific analyses of Minoan fresco samples from Knossos
.
Annual of the British School at Athens
 ,
72
,
121
184
.
Cantisani
,
E.
,
Cecchi
,
A.
,
Chiaverini
,
I.
,
Fratini
,
F.
,
Manganelli Del Fá
,
C.
,
Pecchioni
,
E.
and
Rescic
,
S.
(
2002
)
The binder of the Roman concrete of the Ponte di Augusto at Narni (Italy)
.
Periodico di Mineralogia
 ,
71
,
113
123
.
Carran
,
D.
,
Hughes
,
J.
,
Leslie
,
A.
and
Kennedy
,
C.
(
2012
)
A short history of the use of lime as a building material beyond Europe and North America
.
International Journal of Architectural Heritage
 ,
6
,
117
146
.
Cazalla
,
O.
,
Rodriguez-Navarro
,
C.
,
Sebastian
,
E.
,
Cultrone
,
G.
and
Torre
,
M.J.
(
2000
)
Aging of lime putty: effects on traditional lime mortar carbonation
.
Journal of the American Ceramic Society
 ,
83
,
1070
1076
.
Chandra
,
S.
(
2002
)
Properties of concrete with mineral and chemical admixtures
. Pp.
140
185
in:
Structure and Performance of Cements
 . 2nd Edition. (
J.
Bensted
and
P.
Barnes
, editors).
Spon Press
,
London – NewYork.
Chandra
,
S.
and
Aavik
,
J.
(
1983
)
Influence of black gram (natural organic material) addition as admixture in cement mortar and concrete
.
Cement and Concrete Research
 ,
13
,
423
430
.
Chandra
,
S.
,
Eklund
,
L.
and
Villarreal
,
R.R.
(
1998
)
Use of cactus in mortars and concrete
.
Cement and Concrete Research
 ,
28
,
41
51
.
Charola
,
A.E.
,
Rodrigues
,
P.F.
,
McGhie
,
A.R.
and
Henriques
,
F.M.
(
2005
)
Pozzolanic components in lime mortars: Correlating behaviour, composition and microstructure
.
Restoration of Buildings and Monuments
 ,
11
,
111
118
.
Chatterjee
,
A.K.
(
2002
)
Special cements
. Pp.
186
236
in:
Structure and Performance of Cements
 . 2nd Edition (
J
Bensted
and
P.
Barnes
, editors).
Spon Press
,