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Calcium aluminates in clinker remnants as marker phases for various types of 19th-century cement studied by Raman microspectroscopy

Dariz P, Neubauer J, Götz-Neunhoeffer F, Schmid T (2016)

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Publication Language: English

Publication Type: Journal article, Original article

Publication year: 2016

Journal

Book Volume: 28

Pages Range: 907-914

Journal Issue: 5

DOI: 10.1127/ejm/2016/0028-2577

Abstract

In the second half of the 19th century, Roman and Portland cements played an essential role as active hydraulic binder material in building construction and façade ornamentation. Size and heterogeneous phase assemblage of unhydrated cement clinker remnants in historical cement stone differ significantly from those of remnants occurring in modern Portland cement clinker burnt in rotary kilns due to limitations of the production technology available in the 19th century (e.g., comminution and homogeneity of the feedstock, burning temperature and regime in the intermittently operated shaft kilns, grinding machinery). In the common analytical approach, thin sections and fracture surfaces of historical Roman and Portland cement mortars are characterised regarding their mineralogical composition and microstructure using optical and electron microscopic imaging techniques. Raman microspectroscopy can be additionally employed for petrographic examination, overcoming some limitations of the methods used so far. The determination of the phase content of residual cement clinker grains in the hydrated matrix allows for the differentiation of Roman and Portland cement binders. As marker phases, we propose the calcium aluminates CA, C₁₂A₇, C₂AS and C₃A – besides the commonly used calcium silicates C₂S and C₃S – because of their different formation temperatures and stability fields. This study focuses on the identification of different calcium aluminate and aluminoferrite phases in clinker remnants in samples of cast ornaments of three buildings in Switzerland raised between 1875 and 1893; the obtained Raman spectra are compared with fingerprint spectra of the corresponding pure, synthesised clinker phases collected with the same instrument for an unambiguous data interpretation. In addition to these phases, mainly minerals showing no hydraulic activity, such as, wollastonite CS or rankinite C₃S₂, free lime, portlandite, iron oxides, garnets, augite, albite and feldspathoids have been identified in the sampled historical cement stones by Raman microspectroscopy. As there is a strong relationship between coexisting clinker phases and the chemical composition of the raw meal as well as the burning and cooling history during clinkering, the results can help in understanding the physical and mechanical characteristics of historical cement mortars. This knowledge is fundamental for the choice and the formulation of appropriate repair materials with tailored properties employed in the field of restoration and preservation of the architectural heritage of the 19th and early 20th centuries.

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How to cite

APA:

Dariz, P., Neubauer, J., Götz-Neunhoeffer, F., & Schmid, T. (2016). Calcium aluminates in clinker remnants as marker phases for various types of 19th-century cement studied by Raman microspectroscopy. European Journal of Mineralogy, 28(5), 907-914. https://dx.doi.org/10.1127/ejm/2016/0028-2577

MLA:

Dariz, Petra, et al. "Calcium aluminates in clinker remnants as marker phases for various types of 19th-century cement studied by Raman microspectroscopy." European Journal of Mineralogy 28.5 (2016): 907-914.

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