Evaluating the presence of titanium in XIX-century Brazilian steels by energy-dispersive X-ray fluorescence Augusto Camara Neiva a,n , Herbert Prince Favero Pinto a , Fernando José Gomes Landgraf b a Escola Politécnica da Universidade de São Paulo, Departamento de Engenharia Química, Avenida Professor Luciano Gualberto, Travessa 3, 380 São Paulo, SP, Brazil b Escola Politécnica da Universidade de São Paulo, Departamento de Engenharia Metalúrgica e de Materiais, Avenida Professor Luciano Gualberto, Travessa 3, 380 São Paulo, SP, Brazil HIGHLIGHTS  Ores and products from the XIX Century Ipanema Ironworks were analyzed by EDXRF.  Ti and P detection improved by the use of Cr-tube instead of W-tube.  Detection improved by using detector with multilayer, instead of Zr, collimator.  High Ti and P contents were found in ores and products from Ipanema.  Ipanema ores were found to be very heterogeneous. article info Article history: Received 31 October 2012 Accepted 3 March 2013 Available online 15 March 2013 Keywords: EDXRF Ipanema ironworks Industrial archeology abstract Ores, pig iron and steel pieces from the XIX Century ironworks Royal St. John of Ipanema Iron Foundry (Real Fábrica de Ferro São João do Ipanema), in Iperó, Brazil, were analyzed by Energy-Dispersive X-Ray Fluorescence (EDXRF) spectroscopy, with the aim of investigating the presence of deleterious elements as Ti and P in the minerals and in the resulting products. Analytical modifications made in order to improve the detection limits for Ti and P are discussed. Both elements were found in the raw material and in the products, but large differences in chemical composition were found in different samples or regions of samples. & 2013 Elsevier Ltd. All rights reserved. 1. Introduction Although a small direct reduction ironworks was already installed near São Paulo in the XVI Century, the first larger-scale ironworks in Brazil were created only in the end of the XVIII Century and beginning of the XIX Century. One of the most important of them was the Royal St. John of Ipanema Iron Foundry (Real Fábrica de Ferro São João do Ipanema), installed in the region of the Araçoiaba Hill—an iron-ore, limestone and phosphate deposit, in Iperó, São Paulo state. However, although designed according to the best European models at the time, it has never achieved comparable levels of quality and efficiency. This fact is usually attributed to a high content of deleterious elements in the raw material, especially phosphor and titanium. Calógeras (1904, 1905), for instance, reported the presence of titanium in Ipanema ores, according to analyses made by the laboratories of the Ouro Preto School of Mines (EMOP, Minas Gerais, Brazil), and mentioned the comments of Professor F. Gautier in 1891, who observed cracks in Ipanema cemented bars—bars which had been submitted to surface carburization — and considered them as typically originated by phosphor. The presence of phosphor in Ipanema iron-ores, however, remained a controversial question. Dupré (1885) reported that, according to analyses at EMOP reported by Claude Henri Gorceix, only traces of phosphor were found in the ores, while the soil which surrounded these mineral blocks contained “remarkable amounts of phosphoric acid”. Dupré commented: “where should this phosphoric acid come from, if only traces of phosphor have been found in the mineral, and not even traces were found in the diorite analyzed in the Polytechnic School of Dresden” (translated from Portuguese). This paper presents the analysis of Ipanema ores and products by portable Energy-Dispersive X-Ray Fluorescence (EDXRF) spec- troscopy. As the detection and peak-area determination of some low-content elements, as P and Ti, are very much affected by the experimental setup, the comparison of three different incident beam setups and two different detectors is also presented. 2. Experimental Two spectrometers were used in this work. Spectrometer I uses a water-cooled ItalStructures W-tube (60 kV/1.5 mA maximum) Contents lists available at ScienceDirect journal homepage: www.elsevier.com/locate/radphyschem Radiation Physics and Chemistry 0969-806X/$ - see front matter & 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.radphyschem.2013.03.015 n Corresponding author. Tel.: þ55 11 30912228; fax: þ55 11 30912238. E-mail addresses: acneiva@usp.br, acneiva@gmail.com (A.C. Neiva), herbertpfp@hotmail.com (H.P.F. Pinto), f.landgraf@usp.br (F.J.G. Landgraf). Radiation Physics and Chemistry 95 (2014) 368–372