Bilyana Kostova

The Roman site at Makariopolsko village in Northeastern Bulgaria has been identified as a ceramic production center, featuring single- and double-chamber kilns, abundant ceramic material, and a nearby water source. Geological assessments also reveal local clay deposits. Previous archaeological studies have noted similar Roman production sites in the region, primarily focusing on the study of the kilns and the macroscopic description and classification of the ceramics. However, there has been a lack of research into the pottery’s composition and the sourcing of raw materials, which is essential for understanding the area’s cultural and economic context. This study aims to determine the raw material and firing temperature of the ceramic from the site at Makariopolsko village. Clay samples (both raw and fired at 1100 °C) and ceramic were subjected to chemical, statistical, phase X-ray structural, and thermal analyses. The findings indicate the use of calcareous illite–kaolinitic clay, sourced locally, with an added sandy component. The ceramics were fired at temperatures of 570–760 °C and 920–945 °C. These results, which support the site’s identification as a pottery production center, highlight advanced pottery skills and the dual functional capabilities of the kilns. Additionally, they pave the way for further research into regional production center relationships.

This work studies burned clay plasters from archaeological sites in the cultural-historical region of Sarnena Sredna Gora Mountains and their southern foothills. It was established that the plasters have a similar phase composition, consisting of montmorillonite, muscovite, illite, quartz, albite, calcite and microcline, which indicates that the employed construction system drew resources from a common source or several. Different firing temperature ranges were determined – up to 500 °C; between 500–700 °C; and above 700 °C – up to calcite decomposition temperature (<800 °C). The assumed high temperatures confirm the burning of the archaeological structures, and the varying temperature ranges can be explained by the uncontrollable conditions during the fire.

The production and trade of metals was the foundation of the economic wealth of many regions in the world, which makes the study of ancient metallurgical slags of primary importance. This type of study is relatively new for Bulgaria, where research in the field started in the late 1960s with chemical analysis of copper ore, slags, tools and finished goods from the ancient copper mine in the Ay-bunar area. Iron is one of the most commonly found elements in the earth’s crust and its deposits are widespread, including on Bulgaria’s territory. To this day, however, the study of iron slags from Bulgarian sites through chemical and phase analysis has almost never been explored. The application of these methods allows for the determination of the technology of the ancient metallurgical process. This study investigates iron slags from two Bulgarian archaeological sites, situated in close proximity to the Sarnevets hematite ore deposit, Sarnena Sredna Gora mountain. The ore bodies of the deposit outcrop on the earth’s surface and can be easily recognized due to the red coloring of the soil around them, which is a characteristic trait for finding iron deposits. In addition to the ancient mining activities in the region, proven by over 20 registered ancient mine workings, ancient metallurgical activities were established as well, as proven by the discovered slags. A sample from the hematite ore was studied along with the slags, so that the percentage of iron extracted during the metallurgical process can be determined. The samples were studied through X-ray fluorescence analysis, powder X-ray diffraction analysis, and Mössbauer spectroscopy. The obtained results show that the slags are of the “furnace bottom slags” type, which is a product of metallurgical activity achieved through bloomery technology. The temperature range of the furnaces was determined to be around 900–1100 °C. The reduction of iron was possible at such low temperatures due to the ore’s type—self-fluxing hematite ore. The percentage of iron extracted from the ore was calculated to be between 3.39% and 8.65%. Additionally, a relationship was established between the percentage of extracted iron, the Fe²⁺ content included in wüstite, and the viscosity index of the liquid slag. The acquired results are new to the archaeological studies conducted on Bulgaria’s territory and are a prerequisite for future interpretation and archaeological research.

The aim of this paper is to promote thermal analysis as a method for the study of archaeological ceramics. In order to achieve this goal, the nature of the thermal methods (thermal processes, types of thermal methods and their application) is described. Specific experimental measurements by simultaneous TG/DTG-DSC analysis of ceramic archaeological artifacts are also presented.

Using X-ray fluorescence and Powder X-ray diffraction analysis, the chemical and phase composition of ancient iron slags and raw iron ore were investigated. The type of raw ore was identified as self-fluxing. The operating furnace temperature was determined in the range 900–1000 °C. The results obtained are of archaeological importance. They will contribute to the chronological specification of the time of realization of the metallurgical process and the type of used furnaces.

The advanced tendencies in building materials development are related to the design of cement composites with a reduced amount of Portland cement, contributing to reduced CO₂ emissions, sustainable development of used non-renewal raw materials, and decreased energy consumption. This work deals with water cured for 28 and 120 days cement composites: Sample A—reference (white Portland cement + sand + water); Sample B—white Portland cement + marble powder + water; and Sample C white Portland cement + marble powder + polycarboxylate-based water reducer + water. By powder X-ray diffraction and FTIR spectroscopy, the redistribution of CO₃²⁻, SO₄²⁻, SiO₄⁴⁻, AlO₄⁵⁻, and OH⁻ (as O-H bond in structural OH⁻ anions and O-H bond belonging to crystal bonded water molecules) from raw minerals to newly formed minerals have been studied, and the scheme of samples hydration has been defined. By thermal analysis, the ranges of the sample’s decomposition mechanisms were distinct: dehydration, dehydroxylation, decarbonation, and desulphuration. Using mass spectroscopic analysis of evolving gases during thermal analysis, the reaction mechanism of samples thermal decomposition has been determined. These results have both practical (architecture and construction) and fundamental (study of archaeological artifacts as ancient mortars) applications.