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.     

Multi‐analytical Studies of the Lime Mortars from the Yanxi Hall in the Yangxin Palace of the Palace Museum (Beijing)

For centuries, the architecture of the Palace Museum represented the highest standard of Chinese architecture. The Yangxin Palace of the Palace Museum consisted of 18 masonry buildings built using bricks, wood, roof tiles and various mortars. In 2016, a five‐year project was initiated to work on the maintenance and restoration of the Yangxin Palace buildings. The characterization of the construction materials has become of primary importance, in order to obtain information about the raw ingredients and building technology of the mortars, and the history of possible previous restorations. In this paper, 12 different samples representing three types of mortar‐based materials—namely, jointing mortars between the bricks on the wall, and surface plasters as well as mortars used on the roof—were collected for analysis from the Yanxi Hall of the Yangxin Palace. Analysis into the composition, grain‐size distribution, organic and fibre additives and testing of the mortar density and water absorption were performed. Starch, protein and plant fibres were identified in some of the samples. Brucite, mullite and ettringite were detected within most mortars on the roof, possibly originating from the furnace slag added into the raw materials for restoration purposes. The analytical results will serve as a critical reference for the maintenance and restoration of the buildings in the Yangxin Palace.     

A Multidisciplinary Approach for the Archaeometric Study of Pozzolanic Aggregate in Roman Mortars: The Case of Villa dei Quintili (Rome,Italy)

This contribution focuses on the study of historical mortars from a Roman archaeological site known as Villa dei Quintili, a monumental villa located in the south‐eastern part of Rome (Italy). The study was carried out on 38 mortar samples, collected from several edifices within the complex. A multi‐analytical approach, including polarized optical microscopy, scanning electron microscopy coupled with energy‐dispersive system and laser ablation inductively coupled plasma mass spectrometry, was used to analyse the pozzolanic material used for the preparation of mortars. Data obtained on both major and trace elements were compared with the compositions of Pozzolana Rossa, Pozzolana Nera and Pozzolanella samples from the Alban Hills volcanic district, collected from a historic quarry nearby, as well as with literature data. The results of such a multidisciplinary approach allowed us to recognize the use of all three pozzolan types for the aggregate fraction of examined mortars from the Villa dei Quintili.     

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.     

Historical Mortars from the Fortified Upper Town of Eivissa (Balearic Islands,Spain)

Samples of mortars and stone of Portal de ses Taules from the Renaissance city walls of Eivissa (16th century) were characterized using thermal analysis— thermogravimetry and derivative thermogravimetry (DTG)—x-ray diffractometry, and scanning electron microscopy. The granulometric fraction of particle size <63 μm was selected as representative of the binder, while the fraction 0.5–1 mm was taken as representative of the aggregate in order to characterize mortar samples. The results show that local materials were used. Lime was the main component of most of the samples tested. Thermal analysis revealed the hydraulic nature of the lime mortars. High amounts of sodium chloride were found in the samples analysed.     

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.     

Analytical Investigations of Traditional Masonry Mortars from Ancient City Walls Built during Ming and Qing Dynasties in China

With the development of China’s economy, the protection and conservation of ancient buildings were put on the agenda. However, the current understandings on Chinese traditional mortars are limited and rarely reported in the literature. In this article, the authors investigate seven ancient city wall sites built during the Ming and Qing dynasties (1368–1841 AD) in situ, and subsequently the laboratory analysis were carried out on the collected mortar samples. The characterizations of mortar samples were performed using digital microscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), simultaneous thermal analysis (TG-DSC), as well as wet chemical analysis. The analytical results show that pure lime mortar was widely used in construction during the Ming and Qing dynasties, and it was also a common practice adding sticky rice soup into slaked lime to form sticky-rice lime mortar during preparations. This organic-inorganic composite material could effectively improve mechanical strength of the lime mortar. Moreover, it was first found that the sticky-rice lime mortar sample from Kaifeng ancient city wall contained very fine quartz aggregates, with an approximate binder/aggregate ratio of 1:1. The appearance of this type of mortar probably indicates a great development of Chinese traditional mortars during the mid-19th century.     

故宫博物院旧藏漆器文物中漆灰材质的科学研究

漆灰的修复是漆器文物修复工作的重要组成部分。为揭示故宫博物院旧藏漆器3种典型漆灰的材料构成及特点,以及为漆器修复工作提供科技支持,研究结合X射线荧光光谱、微区X射线衍射、红外光谱、纤维显微镜观测、热裂解-气相色谱/质谱联用等技术,综合分析了3种典型漆灰所含无机及有机原材料。研究结果表明：明代古梅花蕉叶式琴漆灰所用无机材料是动物角灰或骨灰及少量黏土,胶结材料则由中国大漆及少量植物油组成;清代黑漆描金大宝座漆灰的无机材料为含有方解石的黏土,胶结材料为熟桐油、猪血的混合物,此外,样品中还含有麻类纤维,为宝座木胎与漆灰层之间所裱麻布,宝座漆灰不但能提供平整髹漆表面,而且还对麻布有加固定型作用;清代黑漆地填金字张廷玉书圣训天伦对联漆灰的无机材料为黏土,胶结材料则为熟桐油、猪血的混合物。研究所用分析方法体系可实现漆灰原材料,特别是有机胶结材料的准确识别。3种典型漆灰的选材特点与中国古代漆器,特别是明清时期家具、器物制作用料传统相吻合,研究结果可直接应用于漆器文物修复方案的制定。     

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.     

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 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.     

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.     

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)

The paper reports the results of a research project aimed at the characterization of the floor bedding mortars of two Roman houses in Aquileia (north‐eastern Italy), the Domus delle Bestie Ferite and the Domus di Tito Macro. Seventy floor bedding mortars of the two domus were selected and almost half were fully minero‐petrographically characterized by means of optical microscopy operated in transmitted light (OM‐TL), X‐ray powder diffraction analyses coupled with quantitative phase analysis by means of the Rietveld method (XRPD‐QPA) and scanning electron microscopy with EDS microanalysis (SEM–EDS). The results indicate an evolution of the mortar preparation techniques over time in the mosaic of both houses. The materials are compared to the traditional Roman recipes for specific construction techniques.     

Characterization of pozzolanic lime mortars used as filling material in shaped grooves for restoring member connections in ancient monuments

This article presents a set of mechanical characteristics for a pozzolanic mortar consisting of hydrated lime and metakaolin, which is used as filler between metallic connectors and marble blocks during restoration activities of ancient monuments in Greece. Mechanical properties include the uniaxial and triaxial compressive strength, the indirect tensile strength, the bending strength, the elastic modulus and Poisson’s ratio, and a shear failure criterion. Cored cylindrical specimens are used for determining the uniaxial and triaxial compressive behavior and the indirect tensile strength of the mortar, thus ensuring the repeatability of the experimental results. The triaxial tests indicated a plastic behavior of the mortars under study, enabling them to perform well in conditions of high shear forces. Calcite and hydraulic components formed in the setting procedure contributed to the plasticity of the final mortar. The mechanical properties that were developed can be utilized to model material behavior and failure under conditions of confined or triaxial loading. The development of a shear failure criterion for a pozzolanic mortar is a substantial accomplishment that has not been previously reported in the international literature.     

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.     

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.     

A Multidisciplinary Approach to the Study of Archaeological Mortars from the Town of Ammaia in the Roman Province of Lusitania (Portugal)

The Roman town of Ammaia (in Marvão Region) is considered one of the most important recent findings of the Roman presence in Portuguese territory. It was settled in Republican times and abandoned in the seventh century. In this research, 17 masonry mortars and renders from the West Tower (South Gate), the residential area near the West Tower, the macellum, the peristylium, the public bath building, the podium of the temple and the portico of the forum were analysed. The methodology of chemical, mineralogical and microstructural characterization has involved several complementary techniques, including stereomicroscopy, X‐ray diffraction, thermal analysis and scanning electron microscopy coupled with energy‐dispersive X‐ray spectroscopy. The results indicate that the mortars from the beginning of the town's edification were mainly composed of soil (clays). Later, during the main Roman building period, mortars were composed using a calcitic binder and the mortar composition varied according to their use and function. The samples from a period subsequent to the Roman occupation are based on a dolomitic binder. From the present study, relevant information has been acquired about the technological evolution of Roman construction in Ammaia, the historical context of the archaeological structures and guidelines for the conservation and restoration of mortars.     

水硬石灰在花山岩画加固保护中的应用研究

水硬石灰兼具石灰和水泥的优点,低收缩、耐盐、适中的抗压和抗折强度、水溶盐含量低,同时与传统的砖石建筑兼容性好,是一种天然、无污染、耐老化的无机材料。本工作针对花山岩画的开裂特点制订出相应的力学参数要求,配制出两种不同的水硬石灰砂浆,并对这两种砂浆的力学性能进行了分析。同时探讨了不同养护条件对水硬石灰砂浆拉拔强度的影响。现场试验结果说明,填补粘结材料可以提供一定的粘结强度,并且具有使用方便,污染小的特点,可用于花山岩画开裂岩体应急保护加固处理。     

Mineralogical and Mechanical Properties of Masonry and Mortars of the Lucknow Monuments Circa the 18th Century

The Lucknow monuments of the 18th century are large masonry structures built using thin burnt-clay bricks (Lakhauri) and lime-crushed brick aggregate (surkhi) mortars. Investigations were carried out to characterize the engineering properties of old masonry materials and new mortars being used for renovation work. Mechanical properties of reclaimed Lakhauri bricks were found comparable to good quality contemporary bricks of the region. Moreover, X-ray diffraction (XRD) and scanning electron microscopy–energy dispersive X-ray spectrometry (SEM-EDS) analyses indicated that mineralogical composition is not too different, except for few minerals. The lime-surkhi mortar used in old masonry work was found to be lime-rich with binder to aggregate ratio of approximately 1:2 to 3 by volume. The renovation mortar had poor hydraulic property as compared to old mortars indicated by thermal gravimetric analysis–differential thermal analysis (TGA-DTA) analyses. The compressive behavior of multi-wythe recreated Lakhauri masonry prisms was characterized with low compressive strength, low modulus, and significant deformability which result in lower stress demands imposed on the structural assemblages by various environmental forces.     

THE DETERMINATION OF BRICK PROVENANCE AND TECHNOLOGY USING ANALYTICAL TECHNIQUES FROM THE PHYSICAL SCIENCES*†

This work applies established analytical techniques from the physical sciences to Irish brick, in order to gather evidence of ceramic technologies, provenance and sources of raw materials. Petrographic microscopy, X‐ray diffractometry and scanning electron microscopy with an energy‐dispersive X‐ray diffraction attachment were used to study the brick of Rathfarham Castle, Dublin, built c. 1618, where clay brick was introduced in 1771. Local clay was fired in the laboratory and analysed in a similar manner. The petrography of the pointing mortar was studied in order to gather evidence of ceramic provenance. This paper concludes that the brick was hand‐ moulded with a silica‐based, predominantly non‐calcareous clay of glacial origin, gathered locally, including fluxes and a high percentage of non‐plastic material. The mineralogy and petrography of the brick, together with the presence of pebbles and a coarse matrix, suggest that the raw clay was probably gathered from a glacial deposit. The presence of abundant pebbles and colour inhomogeneities suggests a lack of processing of the raw clay. The brick was probably fired in clamps at top firing temperatures ranging from 750°C to above 900°C. Transformation of limestone temper involving the breakdown of calcite and the generation of calcium silicates, and the new formation of plagioclase, high‐temperature quartz, hematite and spinel were revealed. The presence of spinel in ‘hot spots’ indicates that fuel was added to the raw clay in order to assist firing.