Chemical and Phase Reactions on the Contact between Refractory Materials and Slags, a Case from the 19th Century Zn-Pb Smelter in Ruda Śląska, Poland

Abstract

Slags from the historic metallurgy of Zn-Pb ores are known for unique chemical and phase compositions. The oxides, silicates, aluminosilicates, and amorphous phases present therein often contain in the structure elements that are rare in natural conditions, such as Zn, Pb, As. The study focuses on processes occurring on the contact of the melted batch and the refractory materials that build the furnace, which lead to the formation of these phases. To describe them, chemical (X-ray fluorescence (XRF), inductively coupled plasma mass spectrometry (ICP-MS)) and petrological ((X-ray diffraction (XRD), electron probe micro-analyses (EPMA), Raman spectroscopy) analyses were performed on refractory material, slag, and contact of both. Two main types of reactions have been distinguished: gas/fluid- refractories and liquid- refractories. The first of them enrich the refractories with elements that migrate with the gas (Pb, K, Na, As, Zn) and transport the components building it (Fe, Mg, Ca) inward. Reactions between melted batch and refractory materials through gravitational differentiation and the melting of refractories lead to the formation of an aluminosilicate liquid with a high content of heavy elements. Cooling of this melt causes crystallization of minerals characteristic for slag, but with a modified composition, such as Fe-rich pyroxenes, Pb-rich K-feldspar, or PbO-As2O3-SiO2 glass.

Reconstruction of smelting conditions during 16th‐ to 18th‐century copper ore processing in the Kielce region (Old Polish Industrial District) based on slags from Miedziana Góra, Poland

“…proposed by Bachmann (1982) and modified by Ettler et al (2009). This method is widely used in the analysis of smelting slags (e.g., Derkowska et al, 2021;Kupczak et al, 2020;Warchulski, Warchulski et al, 2022) and takes into account the polymerizing to depolymerizing components ratio:…”

“…Derkowska et al, 2021) and Okiep Copper District, South Africa (19th to 21st century; 0.22-0.69;KUPCZAK et al …”

Content of Pb and Zn in Sediments and Hydrobionts as Ecological Markers for Pollution Assessment of Freshwater Objects in Bulgaria—A Review

“…Lead is a heavy metal that has the ability to have a multifaceted toxic effect, even in low doses [ 118 , 119 ]. The reason for this lies in its place in the periodic table, which is determined by its atomic weight and the chemical behavior characteristics of heavy metals.…”

Reconstruction of 16th–17th Century Lead Smelting Processes on the Basis of Slag Properties: A Case Study from Sławków, Poland

“…In the centers of the historical metallurgical industry, we can observe remnants of metallurgical activities in the form of slags. They are a research topic in Poland [8,9] and in other European countries [10][11][12][13][14].…”

“…Based on descriptions contained in such works as De Re Metallica, the methods and devices used for the production of metals can be reconstructed [22]. Production remains such as slags are significant because, in the absence of historical documents on their basis, it is possible to reconstruct the smelting conditions [10,12,13,[23][24][25][26][27][28]. By analyzing their chemical and phase composition, we can recreate the conditions in the historical furnaces.…”