Characterization of ancient building lime mortars of Anhui province,China: A multi-analytical approach

The characterization of lime mortars has become of primary importance in order to obtain information about the raw ingredients and building technology of ancient masonry structures. Five different samples from Anhui province, China, representing two types of lime mortar-based materials: joint mortars between the bricks of the city wall and lime mortar sealing a tomb coffin, were collected for analysis. Archaeological information about the samples was reported and studies into the microtextural features and mineralogical compositions of those mortars were performed via a multi-analytical approach. The joint lime mortars between the bricks of city walls, including Mingzhongdu city wall, Mingzhongdu Xihua gate foundation, Zhengyangguan city wall and She county city wall, were found to be aerial lime mortars. The lime mortar from Nanling Tieguai Song dynasty tomb was analysed and found to be a pozzolanic mortar consisting of lime, clay, sand and cocciopesto-like materials. The analytical results serve as a critical reference for the maintenance and restoration of ancient city walls in Anhui province, and as a starting point for searching for ancient Chinese pozzolanic mortars and technology for making those mortars.     

Historical materials from the post-Cistercian abbey in Kamieniec Ząbkowicki (southwestern Poland)—application of mineralogical methods for identification of source of raw materials

In this paper, we use a set of methods applied for geosciences to reveal the provenance of raw materials and historical aspects of technology of lime production from the post-Cistercian church (southwestern Poland). Two types of building stones (mica schists and sandstones) and two groups of mortars, related with two different construction phases (Gothic and Baroque), were used for construction of the church façade. Principal difference between binding materials involves the presence of Mg-rich phase within Baroque mortars as a result of carbonation of a dolomitic lime whereas Gothic mortars are devoid of hydromagnesite. Mineral composition of the fillers of both mortars is similar, suggesting the same origin represented by local eluvium. Binders of studied mortars are composed of calcite and/or hydromagnesite and rich in lime lumps suggesting incomplete calcination. Studied mortars are weathered which is manifested by presence of gypsum. However, there is no evidence of commonly occurring Mg-rich secondary phases within Baroque mortar probably due to higher solubility of these salts comparing to gypsum. Mineralogical study combined with archeological and geological information enables us to indicate potential sources for the studied building materials. Metamorphic rocks, prevailing within the façade, come from abandoned quarries located in the closest vicinity of the church, whereas sandstones were acquired from the deposits located at a distance of tens of kilometers from the Kamieniec Z?bkowicki. Raw materials used for lime burning were gathered from Przeworno (Gothic mortars) and Z?oty Stok area (Baroque mortars) located approximately 25–30 and 12 km from studied church.     

EVALUATION OF INCLUSIONS IN MORTARS OF DIFFERENT HISTORICAL PERIODS FROM GREEK MONUMENTS*

Mortars were among the first materials used for construction purposes, even from prehistoric times. Their systematic study reveals that they often contained inclusions, which were introduced with the main constituents or added as improvers of mortars' properties. The present study focuses on recording the types of inclusions found in more than 1000 mortar samples of different types (structural, renders and floor mosaic substrates), taken from various monuments of Greece. This extensive study proves that inclusions occur in all types of mortars of all periods and can be distinguished into two categories: those that are added deliberately to mortars to meet specific needs of improvement of their final properties, such as fibrous materials (wood chips, straw); and inclusions that are incorporated into the mass as impurities in the raw materials (lime and clay lumps, shells and probably charcoal particles).     

Hydraulic structures of the Roman Mithraeum house in Augusta emerita, Spain

This paper deals with some of the hydraulic structures of Augusta Emerita (Mérida, Spain), specifically those found in the Mithraeum House. In particular, we describe and characterise the hydraulic mortars and coatings of the viridarium water channel. The recipient of the channel was covered with two hydraulic mortars and a finishing coating. Hydrated lime was used as binder. Calcite grains with different morphology have been observed in the mortars studied. The siliceous aggregate was composed of quartz, mica and feldspars. Ceramic fragments, which were added to the mortar to improve its hydraulic properties, were composed of quartz, mica, iron oxides, anorthite and an amorphous phase; aluminium-iron silicates were used as raw materials for their manufacture. We discuss the interactions between the hydrated lime and the surface of the ceramics in the mortars.     

Characterization of archaeological lime mortars in a Ming dynasty tomb: A multi-analytical approach

Lime mortars have played an important role in constructing ancient Chinese masonry structures, including city walls, buildings, and tombs. A tomb built with lime mortars and stones belonging a Ming high-ranking official, Xu Jie, was discovered in Huzhou City of China. Eight different samples from Xu Jie’s tomb, representing four types of lime-mortar-based materials: joint mortar between stone bricks, bedding mortar, grouting mortar, and plaster mortars were collected for analysis and comparison. The characterization of the construction materials has therefore become of primary importance. The function of each mortar was reported and studies into the micro-textural features and mineralogical compositions of those mortars were performed via a multi-analytical approach. The joint mortars were all found to be aerial lime mortars with predominately lime. The bedding mortar was found to consist of lime, soil and sand, typical of a tabia mortar. The grouting mortar was found to consist of lime and ground contact metamorphosed limestone. Analysis of plaster sample taken from the roof of the main tomb identified the presence of calcium stearate/palmitate, indicating the usage of plant-based tung oil as an additive. The analytical results will promote our understanding of Ming architectural technology and craftsmanship, and provide critical information for the conservation of Xu Jie’s tomb.     

MORTAR STUDIES TOWARDS THE REPLICATION OF ROMAN CONCRETE

The use of strong and durable materials is one essential ingredient leading to the survival of many monumental Roman concrete structures. Replicated concrete mortars with different lime to pozzolan ratios, encompassing the range likely to have been used by the Romans, have been studied here to determine their relative compressive strengths as a function of time. This has been supplemented by the use of the scanning electron microscope to delve into the structure and composition of the binders formed within the strongest and weakest mortars, leading to a deeper understanding of the reasons for the differences in compressive strength.     

GEOCHEMICAL CHARACTERIZATION OF ARCHAEOLOGICAL LIME MORTARS: PROVENANCE INPUTS*

Chemical and mineralogical analyses were carried out on historical lime mortars from the parish church of Santa María La Real (Guipúzcoa). The study included various periods ranging from Roman to modern times and allowed the identification of various types of raw materials. In order to obtain pure binder, free of carbonate aggregates and charcoal particles, an innovative binder separation method was implemented. The chemical composition of the binder allows discrimination of different provenance areas for the raw materials, although those areas do not correlate with specific historical periods. In addition, the influence of burial processes on the primeval chemical features has been assessed and reveals that modern mortars display greater chemical modification than the Roman mortars.     

RADIOCARBON DATING OF MORTARS FROM ANCIENT GREEK PALACES

This study deals with radiocarbon dating of lime mortars which were used as supports for Mycenaean and Minoan paintings. The ¹⁴C dates are. on the whole, compatible with the historical data. and thus show that a large proportion of the Mycenaean surficial coatings can be dated by the radiocarbon method. However. in order to determine the age of the mortars accurately. it is necessary to evaluate the amount of sedimentary carbonate which may have been added to them. It is shown here that the oxygen and carbon isotope compositions of lime mortars are significant indicators that such a mixing actually took place.     

DATING ANCIENT LIME MORTARS BY GEOCHEMICAL AND MINERALOGICAL ANALYSIS

This paper proposes a method of dating based on the study of the mineralogy and geochemistry of lime mortars. If the mortars used in constructing the various parts of a building are made from limestones of distinct geochemistry (minor elements) and mineralogy (clay content), such differences should be identifiable in their compositions. Furthermore, if some parts of the building can be reliably dated, the mortars used in their construction can be compared with mortars taken from parts of the building whose dates are unknown. Under certain conditions, a relationship can be established between the mortars, and a date may be proposed. An experimental procedure, based on identification of mortar phases, is proposed. The method was tested on two historical monuments, built in the eleventh to twelfth and nineteenth centuries respectively, which illustrate different dating problems.     

Chemical and Microscopic Study of Masonry Mortar in Ancient Pagodas in East China

Ancient mortars played a crucial role in the construction of historical architectures due to their physical and chemical compatibility with traditional building materials such as stones and bricks. Therefore, the analysis and optimization of the ancient mortar formula are significant in the restoration and preservation of historical sites. In this work, 20 mortar samples selected from five ancient stone pagodas in Zhejiang Province, China, were analyzed. The results showed that mud, lime-soil mortar, lime-sand mortar, and lime-gypsum mortar were used as binders in these pagodas. The Ca(OH)₂/aggregate ratio ranging from 0.3 to 2.7 was usually used to prepare lime mortar. Protein and polysaccharide were also found in some samples.     

Kinetic effect of carbonic anhydrase enzyme on the carbonation reaction of lime mortar

The effect of carbonic anhydrase enzyme on the precipitation kinetics and phase transformations of calcium carbonate, and on the strength development of lime mortars has been investigated with saturated lime solutions, lime pastes and lime mortars under atmospheric conditions. The results clearly show that carbonic anhydrase catalyzes the reaction between carbon dioxide and aqueous lime, and increases the rate of calcium carbonate crystallization, the yield of the carbonation reaction and mortar strength at early ages. This is most likely a kinetic effect associated with the increased rate of carbonate ions supply to the solution by the enzyme. In addition, this enzyme favors the formation of stable calcite and significantly modifies its morphology by developing new crystal faces. These results suggest a novel approach for accelerating the hardening of lime mortars using carbonic anhydrase enzyme, which may offer a potentially novel approach with significant benefits on the applications of lime mortars in architectural heritage conservation as well as in construction.     

Archaeometric study of natural hydraulic mortars: the case of the Late Roman Villa dell’Oratorio (Florence,Italy)

This paper shows the results of a multidisciplinary study carried out on the mortars from the Late Roman Villa dell’Oratorio (fourth-sixth ad), an aristocratic mansion built in the lower Valdarno (Florence, Italy). Thirty-one bedding mortar and plaster samples were analysed through optical microscopy, thermogravimetric analysis, X-ray powder diffraction and scanning electron microscopy with energy-dispersive X-ray spectroscopy for determining the chemical, mineralogical and petrographic characteristics, while their main physical properties were measured by geotechnical procedures. The collected data indicates that the analysed mortars are made up of very fine to coarse river sand aggregate mixed with white to yellowish-white natural hydraulic lime binder mainly consisting of mixtures of prevailing calcite and hydraulic compounds. With regard to the origin of the raw materials, the aggregates were recognized to be selected Arno river sands, and the binders are the burning product of a local marly limestone (ex Alberese). Therefore, the mortars of the Late Roman Villa dell’Oratorio are one of the first uses of natural hydraulic lime in the lower Valdarno.     

EVALUATION OF BINDER/AGGREGATE RATIOS IN ARCHAEOLOGICAL LIME MORTARS WITH CARBONATE AGGREGATE: A COMPARATIVE ASSESSMENT OF CHEMICAL,MECHANICAL AND MICROSCOPIC APPROACHES*

This paper reports on the comparative evaluation of traditional and innovative methods for the investigation of mortar technology. Preliminary results of various approaches to determining the mix proportions in lime mortars with carbonate aggregate are presented. Quantitative analysis was tested on ad hoc prepared mortars of known composition containing carbonate aggregates of different origin (travertine and Bath limestone). Wet chemical methods, manual disaggregation and Digital Image Analysis of thin sections and cross‐sections stained with Alizarin Red S were tested. The advantages and drawbacks of the different approaches are discussed, and applications to the analysis of archaeological mortars and plasters are highlighted.     

Characterization of Hydraulic Lime Mortar Containing Opuntia ficus-indica as a Bio-Admixture for Restoration Applications

Many successful and long lasting structures that contain lime mortars are hydraulic in nature. Organic admixtures are added to lime mortar mix to modify their fresh and hardened state properties. The present work proposes plant extract as bio-admixture for repair mortar towards the protection of heritage structures. The effect of cactus extract on the properties of hydraulic lime mortar is studied. Mortar´s composition is selected with respect to the composition of historic mortars and modern restoration practice. Cactus extract was added to the lime sand mixture with varying concentrations (25%, 50%, 75%, and 100%) and with different fermentation periods of 0, 1, and 2 days The consistency and workability of modified mortar, mechanical behavior, water absorption, porosity, and water/salt absorption through capillary rise, salt crystallization have been studied. Micro structural properties of the resulting mortar have been evaluated by XRD and FT-IR to identify their mineralogical composition and morphology by SEM-EDX. It is observed that addition of 75% cactus extract with 1-day fermentation produces maximum positive effect on the strength and durability properties of lime mortar. It improves the mechanical characteristics, limits water and salt absorption by capillarity into mortar and also show resistance to salt crystallization cycles.     

New evidence of early use of artificial pozzolanic material in mortars

Hydraulic building composites, such as mortars and plasters, produced with artificial pozzolanic materials, became widely popular thanks to the Romans. Reports on earlier uses of such composites can also be found, mainly in archaeological and historic documents. These date back as far as the time of Minoan and Mycenaean civilizations. Here, we present a holistic analytical investigation of Late Bronze Age mortars from various archaeological sites of Cyprus. We focus on petrographic observations of thin sections, scanning electron microscopy and energy dispersive X-ray microanalyses and we investigate the microstructure and texture of the samples and the chemical composition and interface of their binders. Results of powder X-ray diffraction analyses are also presented, alongside a series of measurements using mercury intrusion porosimetry and vacuum saturation, aiming to estimate the pore size distribution and the physical properties (i.e. open porosity and bulk density) of the specimens under investigation. We also report on tests carried out to assess the drilling resistance of the mortars using a novel, portable system. The results thoroughly confirm, for the first time, the earliest intentional use of crushed brick as an artificial hydraulic additive in lime mortars in Cyprus, in order to enhance their performance and longevity in the absence of natural pozzolanas.     

Characterization of Late Prehistoric Plasters and Mortars from Erimi – Laonin tou Porakou (Limassol,Cyprus)

Several plasters and mortars from the Middle Bronze Age site of Erimi – Laonin tou Porakou (Cyprus) were analysed in order to perform a technological characterization. Morphological (SEM), elemental (EDX), mineralogical (XRPD), petrographic (polarized OM, SEM–EDX), thermal (TGA) and spectroscopic (FT–IR) techniques were applied. Plasters and mortars were identified as pyrotechnological lime products, obtained using local raw materials and containing a moderate amount of spathic calcite fragments. The use of organic fibres was ascertained and a seminal use of a crumbled ceramic as additive was evidenced.     

Cretaceous aggregate and reservoir effect in dating of binding materials

Lime mortars may contain carbon from different origins. If the mortars are made of totally burnt lime, radiocarbon dating yields the true age of building construction. The presence of carbonaceous aggregates gives the so-called dead carbon effect, which may generate older ages. Another source of carbon is charcoal present in mortars. An attempt has been made to apply the radiocarbon method to mortars of archaeologically estimated age from the Dead Sea region. Petrographical analyses of these samples show the carbonaceous character of the binder and large amounts of limestone aggregate. Determination of the mineral composition of the mortars and comparison with the geology of the surrounding, allows the provenance of the raw materials to be identified. They probably represent the Cretaceous rocks of the Judea Group. Separate radiocarbon dates were made on bulk mortar samples, binder, charcoal fragments and separated fractions from mortars. In the case of binder-aggregate mixture the reservoir effect correction has been applied.     

Paper 6: Grouting Mortars for Fragmented Bricks and Repair Mortars for Tiles in the Archaeological Site Coudenberg

Abstract

Different grouting and repair mortars were developed and evaluated for the conservation and restoration of fragmented bricks in the walls and floors of the remaining cellars underneath the Aula Magna, the palace’s main banqueting hall, and to fill the lacunae and perform edge repairs of red and blue-grey ceramic floor tiles in the remaining cellars underneath the chapel of the former Palace of Coudenberg in Brussels, Belgium.

To prevent the deposition of lime bloom at the surface of the masonry and to achieve an acceptable colour match of the grout in harmony with the bricks of the Aula Magna, the effect of brick powder added to natural hydraulic lime was studied. The pozzolanic properties and colour match of several historic and modern powdered bricks were investigated. Surprisingly, ancient bricks do not seem to possess higher pozzolanic properties than the more modern ones, although it is supposed that they were fired at lower temperatures. Additional evidence for the pozzolanic reaction of the different brick powder materials was obtained from a simple visual observation of stored samples. After eight weeks all of the samples containing brick powders, fired at low and high temperatures, added to putty lime had hardened under water and were transformed into a remarkably tough material. These results are important, as modern bricks are readily available in large quantities and different colours, which are hence in favour of being used instead of historical material from the site.

For the repair of the ceramic floor tiles different mortars were investigated with mixtures containing talcum, stone or brick powder, pigments, and chalk added to an epoxy binder. The mortars were tested in the laboratory and in situ for their workability and resemblance with the historic floor tiles. The finished mortars showed excellent aesthetic properties with the tiles in situ and good properties to prevent further loss due to human interaction.     

Paper 5: Historic Mortars from the Coudenberg Archaeological Site: Characterization and Source of Raw Materials

Abstract

The characterization of historic mortars by means of a concise methodology of material analyses can provide crucial information with regard to the origin of the raw materials and the ancient mortar technology. For the analysis of the historic mortars of the Coudenberg archaeological site, the methodology consists of optical and scanning electron microscopy, simultaneous thermal analysis, and an acidic treatment. These analyses were carried out on a total of seventeen samples lifted from various areas in the site, in function of the building chronology resulting from a historic built investigation. The type of binder and aggregate as well as their volumetric ratio were determined.

Both binder and aggregate present distinctive features, which made it possible to identify the probable geological provenance of the raw materials. The observations are verified with available historical records regarding the construction of the main banqueting hall — the Aula Magna — and the use of raw materials such as limestone and sand for the production of lime and construction purposes.     

Materials Characteristics of Roman and Arabic Mortars and Stuccoes from the Patio De Banderas in the Real Alcazar of Seville (Spain)

This study discusses the materials and traditional knowledge used in the manufacture and application of lime mortars and stuccoes by Romans and Arabs in Seville (southern Iberian Peninsula). All of the samples studied contain calcite as a binder, combined with aggregates based on river sand from the filling materials of the Guadalquivir River's depression, located in the vicinity of the Real Alcazar Palace in Seville, Spain, where the artefacts were discovered. The Romans used high‐quality production technology, as evidenced by the careful selection of raw materials as well as by the adequate binder‐to‐aggregate ratio and the elevated homogeneity of the mortars and stuccoes. The suitable distribution of aggregates resulted in higher density values for Roman fragments than for Arabic ones. Results derived from Arabic samples suggest a decline in technology manufacture over time. This work provides useful information, particularly regarding the Roman and Arabic periods in the Iberian Peninsula. The analytical techniques employed in this study were X‐ray diffraction (XRD), X‐ray fluorescence (XRF)—using conventional and portable systems, scanning electron microscopy (SEM), petrographic microscopy, differential thermal analysis/thermogravimetry (DTA/TG), particle‐size analysis and mercury intrusion porosimetry.