Terceira Semana de Engenharia Nuclear e Cincias das Radiaes - SENCIR 2016

Belo Horizonte, 4 a 6 de outubro de 2016

Escola de Engenharia - Universidade Federal de Minas Gerais

Id.: AP-01

USE OF METHODS OF ANALYSIS FOR THE CHEMICAL AND

STRUCTURAL CHARACTERIZATRION OF ZINC COMPOUNDS IN A
FERROUS MATERIAL FROM AN ELETRIC ARC FURNACE

Fernando de Almeida, Arno H. Oliveira, Walter Brito

Universidade Federal de Minas Gerais, Departamento de Engenharia Nuclear

Centro de Desenvolvimento da Tecnologia Nuclear Laboratrio de Difrao de Raios-X
Av. Presidente Antnio Carlos, 6.627 Pampulha / Belo Horizonte/MG CEP 31270-901
peritofernandomg@gmail.com

Key Words: Zinc, Steelmaking Process, Wastes, Methods of Analysis

ABSTRACT

Currently, there is a worldwide priority in developing methods that are ecologically correct for
demarcation of alternatives to the destination of industrial waste that are favorable for the
environment. With this idea in mind, we search for reduction in the use of natural resources,
waste, tailings generation and pollution. Throughout a preventive aspect, several industrial
sectors deal with the challenge of finding cleaner production strategies and with minimal waste
generation. Since the volume of waste is still high, it has become fundamental for industry to
classify their produced waste for the definition of their immediate danger, proper storage
methods, disposition and conduction. In a steel plant perspective, the increase in steel
production to a world wide scale entails greater energy and both renewable and nonrenewable
natural resources consumption, creating a greater quantity of industrial tailings. This work,
therefore, meets this industrial challenge. Our goal is to characterize chemical and structurally
zinc compounds in samples of tailings from a determined electric arc furnace in the steel
treatment processes. Experimental data obtained from Xray fluorescence, Xray diffraction
and electronic microprobe confirm the difficulty of determining how zinc is displaced in the
obtained samples and its possible chemical associations.

1. INTRODUCTION

Steel production, besides consuming nonrenewable resources (mineral goods) and

renewable (air, oxygen, water, etc.) and demanding a large amount of energy (coal,
electricity), generates a considerable amount of industrial waste (slag, mud, gas, dust,
scraps, etc.) [1]. But, investigating steel products life cycle as a whole, one can see a
new situation that contrasts with the impacts generated by the excess of resources
consumption and waste generation. Steel is highly recyclable, has been increasing its
versatility and has been incorporating innovative technologies based on human
intervention in order to reduce or remedy environmental impacts [2].

Although the ironrich waste recycling is widely used, there are still problems inherent
to these wastes that make such process difficult. One important factor is the control of
alkali and zinc contents [3], mainly when the recycling route is directed to the reduction
area. Zinc is present in small quantities in the materials used as furnace load, including
iron ore. For that reason, it is present in steelworks worldwide.
 Terceira Semana de Engenharia Nuclear e Cincias das Radiaes - SENCIR 2016
Belo Horizonte, 4 a 6 de outubro de 2016
Escola de Engenharia - Universidade Federal de Minas Gerais

We present the results of characterization of a steel mill waste from an arc electric
furnace related to chemical and structural aspects by the application of analytical
methods. The analytical processes used in the structural and chemical characterization
of the samples were: Xray fluorescence, Xray diffraction and electronic micro
probing. Such analysis indicated that the compounds with presence of zinc presented a
highly complex geometry and structure.

2. MATHERIALS AND METHODS

2.1. Samples

The analysed samples were supplied by Ecosteel Brasil. They were sampled in the
waste system container and in the electric arc furnaces in a stainless steel production
plant.

2.2. Methods

The following techniques were used:

2.2.1. X-ray Fluorescente

The analysis was made in the facilities of the FRX Service Company, located in Distrito
Industrial Simo da Cunha, in Santa Luzia, Minas Gerais. The used equipment was a
PHILIPS spectrometer, model PW1480 with a rhodium anode. The sample was fused
with lithium tetraborate and the curves were calibrated with both national and
international certification standards (IPP, DCRM, MIST, among others).

For analysis, milling of 100g of material was done, obtained after successive pasterns,
in pan grinders, until material granulometry was below sieve mesh #400 (38m
opening). The used setup was studied with controlled temperature at 105 degrees C;
tungsten carbide mill, 0.075mm sieve, analytical scales, glassware, diverse reagents and
muffle furnace with 1100 degrees of controlled temperature.

2.2.2. Electronic Microprobe

The analysis were made in the Laboratrio de Microanlises from de Physics

Department of UFMG, under the guidance of Professor Ab Cohen Persiano.
Equipment used is a JEOL, JXA8900RL electronic microprobing device, using
wavelength dispersion spectrometry (WDS). Experimental conditions were: acceleration
tension at 20kV and stream current of 25nA. Standards used were natural phases and
pure oxides.

The sample was fitted and polished in successive sandpapers until reaching diamond
paste of 1m.
 Terceira Semana de Engenharia Nuclear e Cincias das Radiaes - SENCIR 2016
Belo Horizonte, 4 a 6 de outubro de 2016
Escola de Engenharia - Universidade Federal de Minas Gerais

2.2.3. X-Rays Diffractoin

The experiments by XRD were made initially in the Laboratrio de Cristalografia from
the Physics Department in UFMG, under the guidance of Alexandre Melo and later in
the Laboratrio de Difrao de RaiosX from CDTN, under Walter de Brito.

The technical specifications and experiment conditions in the analysis made by the
Crystallography Laboratory at Department of Physics at UFMG were:

Xray diffraction by dust method, using a device for polycrystals (BraggBrentano

geometry), by RIGAKU, GEIGERFLEX model, graphite monochromator, 2d = 6.708A.
NaI scintillator detector, Cu xray tube, current intensity 30mA and 40kV tension. Step
at 0.1 degrees and 1.0 second of sampling time. DS (Divergence Slit) = 1, SS (Scatter
Slit) = 1, RS (Receiving Slit) = 0.6mm and RSm (Monochromatic Receiving Slit) =
0.8mm. 4 < 2 < 140. = 1.541874

The technical specifications and experiment conditions in the analysis made by the X
Ray Diffraction Laboratory at CDTN were:

Xray diffraction dust method, using a device for polycrystals (BraggBrentano

geometry), by RIGAHU, GEIGERFLEX model, graphite monochromator, 2d = 6.708A
NaI scintillator detector, Cu xray tube, current intensity 30mA and 40kV tension. Step
at 0.1 degrees and 0.5 seconds of sampling time. DS (Divergence Slit) = 1, SS (Scatter
Slit) = 1, RS (Receiving Slit) = 0.6mm and RSm (Monochromatic Receiving Slit) =
0.8mm. 4 < 2 < 160. = 1.54059

In both experiments, crystalline phases identification was obtained by comparing the x

ray diffraction sample results with the ICDD database (International Center for
Diffraction Data / Joint Committee on Power Diffraction Standards JCPDS, sets 01
58; MDI; Jade 9; 2008).

The analysis made in the Laboratrio de Cristalografia in the DFUFMG was executed
by the following way, with samples separated by distinct granulometries:

gro 38m , 38 < gro 75m and gro > 75m . For each granulometry interval,
the sample was submitted to xray diffraction in the following way: a standard
experiment and an experiment considering the data from Xray fluorescence.

3. RESULTS

3.1. X-ray Fluorescence

The results from the chemical analysis from Xray fluorescence for the investigated
samples main constituents can be seen in Table 01.
 Terceira Semana de Engenharia Nuclear e Cincias das Radiaes - SENCIR 2016
Belo Horizonte, 4 a 6 de outubro de 2016
Escola de Engenharia - Universidade Federal de Minas Gerais

Tab. 01. Results from Xray fluorescence

Substance Concentration Substance Concentration Substance Concentration
(%) (%) (%)
SiO2 3.85 Fetotal 58.18 Na 2 O < 0.10
TiO2 0.063 MnO 1.161 K 2O 0.087
Al 2 O3 0,84 CaO 9.65 P2 O5 0.214
Cr2 O3 0.085 MgO 1.149 ZnO 2,579

Through this analysis, it can be seen the low concentration of zinc, magnesium and
chrome elements. This can already evidence the presence of some of the used inputs as
also the quality of the scrap used in this steel manufacturing process.

The iron is mentioned as total iron, but it can present itself as magnetite, hematite,
wstite, metallic iron and zinc ferrite.

The electrical steelworks dust varies mainly according to the kind of steel to be
produced, besides the nature and quantity of scrap and inputs that constitute furnace
loads. The analyzed scrap has smaller contents of zinc in relation to the dust from
carbon steel production.

The presence of SiO2 possibly occurs from the drag of slagforming agents components
and refractors used.

3.2. Electronic Microprobe

Initially, we set the system to generate elemental distribution maps to obtain spatial
distribution information from the following elements: aluminum, calcium, silicon, iron
and zinc in a given samples area.

Then, we use the maps to make images with retrospread electrons and locate heavier
phases in relation to lighter ones. In the images, phases in lighter gray tones have higher
average atomic numbers than the ones in darker grey tones [4]. Thus, we can see the
compositions differences between presented phases.

We elaborated also images of secondary electrons and those emphasize the difference in
the sample shape and relief.

Also, we obtained EDS energy spectrum images, where we had energy by intensity
(keV x cps).

The images from energy spectrum by EDS and the images from WDS suggest the
presence of iron oxide phases, one being with a small content of zinc, suggesting the
 Terceira Semana de Engenharia Nuclear e Cincias das Radiaes - SENCIR 2016
Belo Horizonte, 4 a 6 de outubro de 2016
Escola de Engenharia - Universidade Federal de Minas Gerais

formation of zinc ferrite; phases with zinc oxide; phases with silicon and phases with
calcium.

The map for zinc shows that it is distributed in a diffuse shape in the tested area, but
with low content. The regions where the presence of silicon and calcium were higher,
the presence of iron was smaller.

There are regions where is common to see iron and zinc, showing the existence of the
ZnFe2 O4 phase.

It is also possible to identify places where zinc was not present and iron shows itself in
greater content, suggesting the presence of iron oxides, like magnetite.

Due to the mapping results, one can see that calcium was distributed in the sample
distinctly. Calcium was seen in greater contents where iron was not present at all. In this
region, silicon was also present in high concentrations.

Probably this was some phase rich in calcium and silicon from the slagforming agent
added in the steel manufacturing process that has these elements in its composition.

The calcium content evaluated by Xray fluorescence is 9.85%. Considering this value
and the distribution in regions with greater concentrations and smaller iron contents, it
was possible that calcium showed itself in distinct phases. Some studies show the
presence of calcite and dolomite in the dust from electrical steelworks [5].

The use of refractors, iron alloys, pig iron, slagforming agent and scrap justifies the
presence of this huge variety of chemical elements in the dust. The presence of silicon
where iron was in high concentration can happen with ironalloy (Fe Si ) dragging
used in the process.

According to the images from secondary electrons, one can see the morphology with the
presence of irregular shaped particles, both plain and others with dendritic phases in its
interior. These dendritic structures were related to the cooling speed suffered by the
particles since the moment they were ejected from de liquid metal [6].

3.3. X-ray Diffraction

We have obtained the diffraction patterns in the performed analysis at the Departamento
de Fsica at UFMG and Laboratrio de Cristalografia at CDTN.

After obtaining the graphs, we generated the database from an identification program
("MATCH") explaining the possible phases found for each particle size range. In this
program the indicator of the degree of similarity between a test result and the database
is given by the "FigureofMerit" (FoM).
 Terceira Semana de Engenharia Nuclear e Cincias das Radiaes - SENCIR 2016
Belo Horizonte, 4 a 6 de outubro de 2016
Escola de Engenharia - Universidade Federal de Minas Gerais

By analyzing the diffraction patterns obtained for the three ranges of grainsize and
their generated tables, we have observed that the three analyzes were extremely similar.

The stages identified in these analyzes were: elemental iron, elemental zinc, manganese
dioxide, quartz, magnesium oxide and calcium oxide.

Analyzing the constitution of inputs used in the process, the literature and the results of
Xray fluorescence analysis and electron microprobe, we could expect the presence of
the following stages: calcium oxide, magnesium oxide and quartz. The presence of
elemental iron was also expected due to its high content in the sample, and elemental
zinc, observed in the microprobe analysis to be very diffuse, was also expected.

However, the ferrous oxide stages were not identified and therefore it was necessary
further analysis by xray diffraction varying detection limits.

The Xray diffraction patterns of stages Fe3 O4 and ZnFe2 O4 were similar. There were
also similarities with the arrangement Zn Mn Fe2 O4 , however, it was unlikely the
formation of this structure due to the low Mn content in the analyzed sample. The
individualization of these phases in a sample is unclear, it can however be evaluated
through additional analyzes.

Zn0,945 Fe1, 78 O3, 71 and Zn0,984 Fe1,968 O3,938 are structures with diffraction patterns similar to
the stages Fe3 O4 and ZnFe2 O4 .

Zn0, 2 Mn0,8 Fe2 O4 , Zn0, 4 Mn0, 6 Fe2 O4 , Zn0, 6 Mn0, 4 Fe2 O4 , Zn0,8 Mn0, 2 Fe2 O4 and
Zn0,9 Mn0,1 Fe2 O4 are stoichiometries which present the same diffraction pattern graph
[7].

The diffraction line 7,979 is suggested to the Fe(OH , Cl ) stage with uncertainties,
which may also be consistent with the Zn5 (OH )8 .Cl 2 H 2 O structure. In some structural
characterization through the Xray diffraction technique studies, several authors have
observed the presence of ZnO and ZnFe2 O4 stages [5], which can be seen also in the
diffractogram obtained from our analysis.

With the data obtained from the generated diffractogram, we described crystalline
stages.

4. CONCLUSION

The results obtained relating to the characterization of this ferrous material led to the
following conclusions:

the major constituents of the analyzed sample are metallic iron and wstite;
 Terceira Semana de Engenharia Nuclear e Cincias das Radiaes - SENCIR 2016
Belo Horizonte, 4 a 6 de outubro de 2016
Escola de Engenharia - Universidade Federal de Minas Gerais

the XRD technique has detected the presence of the following stages: Fe , FeO ,
Si , SO2 , Fe3 O4 , ZnFe2 O4 , FeO.OH , CaCO3 , Fe2 O3 , Fe(OH )Cl , CaMg (CO3 )2 ,
FeSi , NaCl , ZnO , MgO , CaO and MnO2 ;
zinc is associated with the zincite ( ZnO ) and franklinite ( ZnFe2 O4 ) stages and
is found diffused in the low concentration sample;
due to limitations of trial conditions, it was not possible to obtain the
concentration of zincite and franklinite;
in the regions where the presence of silicon and calcium were more intense, the
presence of iron was smaller.

5. ACKNOWLEDGEMENTS

I would like to gratefully thank to my PhD advisor, Professor Arno Heeren Oliveira for
supporting me during these masters program. I also would like to gratefully thank to
Walter Brito for his guidance and help on the XRD analysis.

I thank so much the UFMG (Departamento de Engenharia Nuclear and Departamento

de Fsica), CDTN (Laboratrio de Difrao de RaiosX) and the people who were not
part of this program but helped me out.

And then I also thank to EcoSteel do Brasil for providing me as much samples as I
needed in this work and the free admission in its industrial facilities.

6. BIBLIOGRAPHICAL REFERENCES

[1] MCGANNON, The making, shaping and treating of steel, 11th ed., Steelmaking and
refining Volume, Warrendale, PA, EUA, AISE Steel foundation, pp. 204-211 (1998).

[2] MUCAR CARBON COMPANY, The Evolution of arc furnace, highlights of new
technologies. Columbia (2001).

[3] OZTURK B., FRUEHAN R. J., Vaporization of zinc from scrap, Stellmaking
Conference Proceedings, Warrendale, PA, EUA, pp. 586-592 (1996).

[4] ANDERSEN, C.A., Microprobe analysis, New York., John Wiley (1973).

[5] MORI, K., Kinetics of fundamentals reactions pertinent to steelmaking process, V.28,
Tokyo, Iron Steel Institute of Japan, v.28, pp. 261-346 (1988).

[6] NYRENDA R. L. The processing of steelmaking flue-dust: a review, Minerals

Engineering, v.4, 1991, 1002-1025 (1991).

[7] AZAROFF, L., BURGER, M.J., The powder method in x-ray crystallography, McGraw-
Hill Company, New York (1958).