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Faculty of Forestry, Geosciences and Hydrosciences Institute of Waste Management and Contaminated Sites Chair in Waste Management Prof.

Dr.-Ing. habil. B. Bilitewski

Mineral phases of steel industry slags used in a landfill cover construction

MASTER THESIS TECHNISCHE UNIVERSITT DRESDEN

Submitted by: Silvia Diener Matriculation number: 2800 264 Tutors: Dr.-Ing. Lale Andreas, Division of Waste Science & Technology, Lule University of Technology, Sweden. Prof. Dr.-Ing. habil. Bernd Bilitewski, Institute of Waste Management and Contaminated Sites, Technische Universitt Dresden, Germany. Dresden, the 21st of March 2006

Aufgabenstellung fr die Diplomarbeit


Thema: Mineralphasen in Stahlschlacken beim Einsatz in der Dichtungsschicht einer Deponieoberflchenabdichtung (Mineral phases of steel industry slags used in a landfill cover construction) Pfannenschlacke und Elektroofenschlacke sind Abfallprodukte aus der Stahlindustrie. Die derzeitige Praxis besteht in einer Deponierung dieser Stahlschlacken. Je nach Stahlwerk fallen jhrlich Tausende Tonnen verschiedener Schlacketypen an. Der Einsatz dieser Schlacken beispielsweise als alternative Baustoffe im Deponiebau wird in Zukunft strkere Bedeutung und Akzeptanz erfahren. Durch die zementhnlichen Eigenschaften von Pfannenschlacke nach Zugabe von Wasser und anschlieender Verdichtung rcken Einsatzgebiete bei denen hohe Dichte, niedrige Permeabilitt und mechanische Stabilitt vonnten sind, in den Vordergrund, beispielsweise in der Dichtungsschicht einer Deponieoberflchenabdichtung. Die zu untersuchenden Stahlschlacken stammen von Uddeholm Tooling AB, einem Stahlwerk in Hagfors, Schweden.

Zielsetzung: 1) die Untersuchung der Abbindeeigenschaften von Pfannenschlacke, Elektroofenschlacke und Mischungen aus denselbigen durch kalorimetrische Messungen, 2) die Untersuchung der kristallinen und amorphen Mineralzusammensetzung der Schlackeproben mit Hilfe IR-Spektroskopie und Rntgenbeugung, 3) die Auswertung der Ergebnisse im Hinblick auf Langzeitverhalten und Stabilitt der Mineralphasen sowie 4) die Analyse einer mglichen Korrelation zwischen Abbindeeigenschaften und Mineralzusammensetzung der Materialien.

TABLE OF CONTENTS

II

TABLE OF CONTENTS LIST OF ABBREVIATIONS .......................................................... III LIST OF FIGURES........................................................................... V LIST OF TABLES ......................................................................... VII TERMINOLOGY .................................................................................... VIII SUMMARY ............................................................................................. XIII 1 INTRODUCTION...................................................................................... 1 2 MATERIAL AND METHODS ................................................................. 2
2.1 Material....................................................................................................................... 2 2.2 Methods ...................................................................................................................... 5 2.2.1 Calorimetry ...................................................................................................... 6 2.2.3 X-ray diffraction .............................................................................................. 7

3 RESULTS................................................................................................... 8
3.1 Calorimetry ................................................................................................................. 8 3.2 IR spectroscopy........................................................................................................... 9 3.3 X-ray diffraction ....................................................................................................... 13

4 DISCUSSION .......................................................................................... 15 5 CONCLUSIONS...................................................................................... 22 6 REFERENCES......................................................................................... 25

APPENDICES APPENDIX I APPENDIX II Sample preparation and Measurement Data Steel slags - General data, mineralogical composition and suitable analysis methods for determining heat of hydration and mineral phases - Literature Review Extended summary in German Mineralphasen in Stahlschlacken beim Einsatz in der Dichtungsschicht einer Deponieoberflchenabdichtung

APPENDIX III

LIST OF ABBREVIATIONS

III

LIST OF ABBREVIATIONS
AOD BF BOF CEN DRIFTS DTA EAF EDX FEhS Argon Oxygen Decarburisation Blast Furnace Basic Oxygen Furnace (LD converter) Comit Europen de Normalisation (European Committee for Standardization) Diffuse Reflectance Infrared Fourier Transform Spectroscopy Differential Thermal Analysis Electric Arc Furnace Energy Dispersive X-Ray Analysis FEhS - Institut fr Baustoff-Forschung e.V. (former Forschungsgemeinschaft Eisenhttenschlacken; German research institute for building materials) FTIR KBr MID-IR IR MSWI NMR OECD OPC SEM TG/TGA XRD Fourier Transform Infrared (Spectroscopy) Potassium Bromide Mid range of infrared radiation Infrared (Spectroscopy) Municipal Solid Waste Incineration Nuclear Magnetic Resonance Organisation for Economic Co-operation and Development Ordinary Portland Cement Scanning Electron Microscopy Thermal Gravimetric Analysis X-Ray Diffraction

A special cement nomenclature, called cement chemist notation (CCN) is used to simplify cement formulas. Important abbreviations are: C = CaO S = SiO2 A = Al2O3 F = Fe2O3
S = SO3

lime (calcium oxide) silica (silicon oxide) aluminate (aluminium oxide) ferrite (iron oxide) sulphate (sulphur oxide)

LIST OF ABBREVIATIONS

IV

H = H2O C-S-H C-A-H

in cement: hydrated water Calcium silicate hydrate Calcium aluminate hydrate

With the help of that nomenclature, formulas as for the mineral ettringite 6CaO*Al2O3*3SO3*32H2O can be written simpler as C6A S 3H32.

LIST OF FIGURES

LIST OF FIGURES
Figure 1. EAF slag ............................................................................................................ 2 Figure 2. Ladle slag .......................................................................................................... 2 Figure 3. Chemical composition of EAF slag and ladle slag............................................ 3 Figure 4. Particle size distribution of EAF 1, EAF 2 and ladle slag (Herrmann et al., 2005) ..................................................................................... 4 Figure 5. Sample cup in the calorimeter ........................................................................... 6 Figure 6. Temperature changes per gram slag during hydration measured with calorimetry ........................................................................................................ 8 Figure 7. IR spectra of 100 % ladle slag (hydrated sample)............................................. 9 Figure 8. FTIR spectra of two hydrated slags and three hydrated slag mixtures ........... 10 Figure 9. Comparison of area ratio of peaks caused by absorption of OH-bonds.......... 11 Figure 10. Diffraction pattern of 100 % ladle slag and 100 % EAF slag ....................... 13 APPENDIX I Figure 1. IR spectra for all hydrated slag samples (LS = ladle slag)................................ 8 Figure 2. IR spectra for hydrated ladle slag and non hydrated ladle slag......................... 9 Figure 3. IR spectra of 100 % EAF slag and 100 % ladle slag (hydrated) ....................... 9 Figure 4. Diffraction pattern of 100 % ladle slag and 100 % EAF slag ......................... 10 APPENDIX II Figure 1. Flow chart of the steel making process at Uddeholm Tooling Ltd. (Beskow and Du Sichen; 2004)......................................................................... 3 Figure 2. Types of steel slags generated in Europe 2004 (Euroslag, 2006) ................................................................................................ 5 Figure 3. Utilisation of steel slags in Europe 2004 (Euroslag, 2006)............................... 6 Figure 4. Reuse of steel slags in Germany in 2004 (FEhS, 2005).................................... 7 Figure 5. Layers and their functions in a cover construction with a mineral liner; examples for possible alternative materials (Andreas et al., 2005)................... 8 Figure 6. Changes in cement microstructure during hydration (Wenk and Bulakh, 2004) ........................................................................................................................................ 15 Figure 7. Phase diagram of CaOSiO2Al2O3 system.................................................... 17

LIST OF FIGURES

VI

Figure 8. Differential calorimetric analyses of CA, CA2 and corresponding mixtures (Mhmel et al., 1998)...................................................................................... 19 Figure 9. Compilation of literature data about main elements in EAF slags (BMU data [6])................................................................................................ 21 Figure 10. Composition of Uddeholm ladle slag and BMU data about ladle slag [6].... 23 Figure 11. Mineralogical evolution taking place during weathering of MSWI bottom ash (Piantone et al., 2004)................................................................... 26 Figure12. The rate of heat evolution of cement hydration at 25 C (Mostafa and Brown, 2005) ............................................................................ 30 Figure 13. X-ray diffraction of EAF sample (Shen et al., 2004) .................................... 34 Figure 14. Vibration modes of the CO2 molecule .......................................................... 37 Figure 15. Schematical draw of the Michelson interferometer ...................................... 39 Figure 16. Comparison of interferogram and spectrum.................................................. 40 Figure 17. Sample accessory of the DRIFTS method .................................................... 40 Figure 18. Model spectrum for explaining fundamental terms (Gnzler and Gremlich, 2002) ........................................................................ 42

LIST OF TABLES

VII

LIST OF TABLES
Table 1. Annual slag generation at Uddeholm Tooling Ltd (Herrmann et al., 2005)....... 3 Table 2. Mixtures of EAF and ladle slag used in the experiments ................................... 4 APPENDIX I Table 1. Sample data......................................................................................................... 2 Table 2. Recorded data of 100 % ladle slag sample ......................................................... 2 Table 3. Recorded data of 35 % EAF slag sample ........................................................... 3 Table 4. Recorded data of 50 % EAF slag sample ........................................................... 3 Table 5. Recorded data of 65 % EAF slag sample ........................................................... 3 Table 6. Recorded data of 100 % EAF slag sample ......................................................... 4 Table 7. Mixtures for preparation of specimens ............................................................... 5 Table 8. Data of the cylinder ............................................................................................ 5 Table 9. Data of modified Proctor device......................................................................... 5 Table 10. Main IR peaks of 100 % EAF slag, 50 % EAF slag and the two ladle slag samples including literature data .................................................................................... 11 APPENDIX II Table 1. Steel slag generation in EU, Germany and Sweden ........................................... 6 Table 2. Clinker and mineral phases in OPC according to Knoblauch and Schneider (1992).......................................................................................... 12 Table 3. Main mineral phases in cement with chemical compounds and corresponding cement nomenclature.......................................................................................... 14 Table 4. Hydraulic behaviour or different materials (Rhling et al., 2000) ................... 16 Table 5. Chemical composition of certain materials used in cement industry (according to Knoblauch and Schneider, 1992) ................................................. 17 Table 6. Chemical composition of two EAF slags (Motz and Geiseler, 2001) .............. 20 Table 7. Predominant mineral phases associated with steel slag (Murphy et al., 1997).......................................................................................... 22 Table 8. Regions of Infrared radiation............................................................................ 35

TERMINOLOGY

VIII

TERMINOLOGY
Amorphous Minerals that have no crystal lattice, i.e. no structure consisting of crystal units. The antonym is crystalline. Blast furnace In a blast furnace, iron ore is reduced to iron in the form of pig iron. Raw materials are coke and iron ore. Furthermore, air is blown into the furnace. Products of this continuous process are molten iron and blast-furnace slag. Carbonation Chemical reaction leading to formation of carbonates. An example is the reaction of calcium hydroxide with carbon dioxide in the air to calcite. Cash minerals Minerals that have the ability to incorporate heavy metals in their crystal structure (also called reservoir minerals). They can be formed by thermal processes (primary cash minerals) or by hydraulic reactions (secondary cash minerals). Certain cement phases, carbonates and iron-hydroxides are known as cash minerals. Curing Diffraction Hardening of cement due to hydration. When a beam of light is directed towards a crystal, light is diffracted under a certain conditions, e.g. that distances between the crystal lattice are equivalent to the wavelength of the light beam. Diffraction means that the light of the original light beams is scattered, many beams are formed that all have a regular pattern including information about the crystal structure.

TERMINOLOGY

IX

Fly ash

Artificial puzzolan originating from coal combustion or MSWI incineration. Fly ash is collected in electric filters and bag filters.

Hydration1

The curing of cement and cementitious materials directly after addition of water is based on the chemical and physical integration of water in the structure of hydraulic minerals. Chemically bound water cannot evaporate and belongs to the hardened cement paste, whereas physically bound water present in e.g. capillary pores can evaporate.

Ladle Latent hydraulic

A vessel for transporting molten steel or metals. Property of calcium silicate aluminate compounds. After addition of water, hydration takes place but just in presence of an activator, e.g. Ca(OH)2. An example for a material consisting of calcium silicate compounds is blast furnace slag. The cause for this property is a defective (metastable) lattice structure (Knoblauch, 1992).

Liner

A liner is a designed containment layer. It can be built from natural or synthetic materials. Here, the term is used for a part in the top cover construction of a landfill, also called the barrier layer.

Mineral phase

A phase is any part of a system that is physically homogeneous within itself and is mechanically separable from the other parts. Any pure mineral is a single phase; any rock is a system in which the phases are the individual minerals. In cement for example the main mineral phases are tricalcium silicate, dicalcium silicate, tricalcium aluminate and tetracalcium alumino ferrite.

German: Hydratation

TERMINOLOGY

Molecular vibrations

The chemical bonds of a molecule will vibrate, if a molecule absorbs infrared radiation. The bonds can perform different vibrations. They can stretch, bend and contract. Therefore, infrared spectroscopy belongs to the methods of vibrational spectroscopy.

Puzzolanic materials

Natural or artificial materials that - together with water and the activator calcium hydroxide (slaked lime) - form cement stone similar products. Beneath alumina, puzzolans generally contain silica amounts between 50 and 80%. The silica is present in an amorphous state, otherwise no reaction would occur. Puzzolans just form a hydraulic binder after the chemical reaction with calcium hydroxide. The activator calcium hydroxide is needed for the hydraulic reaction of puzzolanic materials even if there is enough calcium oxide present in the material to build the same hydration products. They are therefore distinguished from hydraulic or latent hydraulic substances. The reaction rate for a puzzolanic reaction is slower than for a hydration reaction (Grbl et al. 2001).

Solid solution2

According to IUPAC (1997), a solid solution is a mixed crystal. Another constituent - apart from the ones belonging to the original crystal - must be present that fits into the crystal structure and is distributed in the host crystal.

Steel slags

Also called steelmaking slags. The term includes EAF slags, ladle slags and AOD slags. They are formed during steel production by adding slag formers. The slag formers react with the undesirable elements, e.g. carbon, silicon, sulphur or phosphorous. These elements are oxidised and rise to the

German: Mischkristall

TERMINOLOGY

XI

surface of the molten steel, where they are removed (deslagging). Tapping of steel Here: The process of pouring the steel from the EAF furnace into the ladle. Uphill casting For solidification, different steel casting processes exist. The typical ingot mould casting process is known as uphill casting, in which molten metal fills a mould from the bottom. Vacuum degassing After the steel has been treated in the ladle, the ladle is brought to a degassing station where it is put under a vacuum lid. The vacuum treatment and the additional stirring with injected argon gas or blowing of oxygen shall a. o. reduce several elements as e.g. hydrogen in the steel.

PREFACE

XII

PREFACE
I would like to express my gratitude to Dr. Lale Andreas for giving me not only the opportunity to write this thesis at Lule University of Technology (LTU), but also for helpful answers to all my questions, the organization of my stay, the supervision of this thesis and her efforts to make me settle in. I thank Prof. Dr.-Ing. habil. Bernd Bilitewski for being my supervisor in Dresden. I also thank Inga Herrmann for her help, for her correction tips and last but not least for bailing me out at Christmas 2005. The master thesis was performed in co-operation with the division of process metallurgy at LTU. For the laboratory analyses, data interpretation and sharing their knowledge about metallurgy and minerals, I especially thank Margareta Lidstrm Larsson and Fredrik Engstrm. I really enjoyed my stay at the division of Waste Science and Technology in Lule and always felt a very friendly atmosphere there. Therefore, I want to thank Roger Lindfors, Ulla Brit Uvemo, Igor Travar, Lisa Dahln, Dr. Holger Ecke and Prof. Dr. Anders Lagerkvist. Furthermore, I got to know a lot of friends in Lule who tried to make me see the things besides work and studies. I also thank Rita Ougolnikova and Irene Schneider for last comments on this work. I thank my family, for their continual support in everything that I do. I will always be grateful to you.

SUMMARY

XIII

SUMMARY
In 2004, the European steel industry generated about 15.2 million tonnes of different steel slags. Out of these, electric arc furnace (EAF) slags and secondary metallurgical slags account for almost 6 million tonnes (Euroslag, 2006). Steel slags can potentially be reused, e.g. as construction material in landfill liners or cover constructions. Their physical and chemical properties have been investigated by e.g. Herrmann et al. (2005), Shen H. et al. (2004), Shi (2002), Motz and Geiseler (2001) and Fllman (1997). However, not much is known with regard to their long-term behaviour. The presented project deals with alterations of the mineralogical composition of steel slags as a base for estimations of the long-term stability. Two types of steel slags, electric arc furnace (EAF) slag and ladle slag were mixed in different proportions and analysed with calorimetry, infrared (IR) spectroscopy and Xray diffraction (XRD). In the mixture ladle slag reacts with water by hydration, while the EAF slag works as filler. The study focused on the cement reaction as well as on the mineralogical composition. The cement reaction was tested with the aid of calorimetry, whereas IR spectroscopy (FTIR spectrometer) and XRD were used to analyse the amorphous and crystalline mineral phases. A method for preparing specimens was developed. The temperature development of the different mixtures of EAF and ladle slag recorded by the calorimeter showed an activation of the mixture by Al-rich ladle slag: higher portions of ladle slag resulted in an increased development of heat. However, higher portions of ladle slag also involve a delay of the maximum heat build-up. The IR analyses showed that changes in the sample spectra were proportional to the content of EAF slag. Additionally, one IR analysis of non-hydrated (dry) ladle slag was performed. During qualitative analysis of the IR spectra, absorption bands were identified in the wave number ranges of inorganic carbonates, calcium silicates and aluminium oxide. The biggest differences between the samples could be seen in the region from 3500 to 3200 cm-1. Ladle slag showed clear absorption peaks, while EAF slag did not. This wave number range represents the absorption of O-H bonds and therewith the integration and absorption of water molecules in the mineral structure.

SUMMARY

XIV

With the help of XRD, the main minerals in a 100 % ladle slag were identified as

- Calcium silicate ( -Ca2SiO4) and Mayenite (Ca12Al14O33), whereas Merwinite


(CaMgSiO4) and Monticellite (Ca3Mg(SiO4)2) were most common in 100 % EAF slag. New mineral phases after mixing both slag types could not be detected with XRD. Mineralogy determines steel slag properties and liner performance. Mineral alterations include the formation of secondary minerals through weathering of the analysed primary minerals. Estimations for these aging reactions of primary minerals are outlined.

INTRODUCTION

1 INTRODUCTION
Electric arc furnace (EAF) slag and ladle slag are by-products of steel produced in an electric arc furnace and the following secondary metallurgy processes in a ladle vessel. Their reuse is not only of environmental benefit as natural aggregates do not have to be exploited, but also of economical benefit as many landfills in Europe need a final cover in the future. In order to assess if EAF slag and ladle slag can be utilised as construction materials in the liner barrier of a landfill, their physical and chemical properties have to be known, as well as their environmental impact and long-term behaviour. The mechanical and chemical stability of the construction is an important question. The aims of the study are to estimate the reactivity of the slags after water addition, to determine amorphous and crystalline mineral phases in the slags and slag mixtures, and to evaluate the stability of the major mineral phases. Another question is the formation of new mineral phases after mixing EAF slag with ladle slag and water. The reactivity of the slags after water addition is together with the gradient of heat generation over time an indicator for the formation of more or less stable mineral phases during the curing process. The stability of the steel slag minerals is important for the prediction of mineral transformations that may occur in a landfill environment and therewith affect the stability and long-term behaviour of the cover construction itself. The suitability of the analysis methods calorimetry, IR spectroscopy and X-ray diffraction (XRD) for answering the above stated research questions was assessed in a literature review (Appendix II). A method to prepare samples for IR and XRD analyses was developed and is described in Appendix I, together with the sample preparation for the calorimetric experiments and the collected data.

MATERIAL AND METHODS

2 MATERIAL AND METHODS


In the following chapter, the well-known properties of the steel slags are reported about. In addition, the measuring procedure of the various analytical techniques is described.

2.1 Material
Five steel slags were sampled from Uddeholm Tooling Ltd., a company producing a. o. high-alloyed tool steel. The slags were investigated at the Division of Waste Science and Technology at Lule University of Technology (LTU) during autumn and winter 2004/05. The results of these investigations are published in Herrmann et al. (2005) and Andreas et al. (2005) yet those results being important for the understanding of this study are shortly described in the following. Two EAF slags and one ladle slag were investigated in this study, whereas both EAF slags (called type 1 and 2) are mixed in equal shares due to their similar chemical composition. Figure 1 and 2 show the two steel slag types.

Figure 1. EAF slag

Figure 2. Ladle slag

The investigated EAF slag and ladle slag had some major differences in their chemical composition, which is presented in Figure 3. Not only does ladle slag contain 26 % more calcium oxide and 47 % more aluminate, it also reaches only 39 % of the silicate content of EAF slag.

MATERIAL AND METHODS

45 40

Electric Arc Furnace slag 1/2 Ladle slag

content [wt.-%]

35 30 25 20 15 10 5 0

CaO SiO SiO2 Al2O3 MgO CaO Al 2 2O3 MgO

MnO Fe2O3 FeO MnO Fe2O3 FeO

Figure 3. Chemical composition of EAF slag and ladle slag EAF 1 was produced under reducing conditions while there was still a high silicon content in the steel melt. EAF 2 was formed under a reducing atmosphere as well, but with addition of silicon and iron chromate (FeCr). Furthermore, oxygen was blown into the melt. The ladle slag was tapped after the secondary steelmaking process at the ladle furnace station. In the ladle, a. o. processes as deoxidisation with aluminium, addition of slag formers (dolomite and lime) and alloys take place. The production steps in the EAF and in the ladle are further explained in Appendix II (Chapter 2). Uddeholm Tooling Ltd. is a small steel mill. The annual slag output can be seen from table 1. Table 1. Annual slag generation at Uddeholm Tooling Ltd (Herrmann et al., 2005) EAF 1 EAF 2 LS amount per year [ton] 5200 2000 1300

After tapping, the slag is stored indoor and just cooled by air contact. The slag types are piled separately. A representative sample was taken from every heap in summer 2004. EAF 1 and 2 were crushed to a size smaller than 20 mm. They contain much coarser particles than the ladle slag which disintegrates into fine powder because of the high Ca/Si ratio. As can be seen in Figure 4, two thirds of the ladle slag consists of particles smaller than 0.25 mm, while only 18 to 24 % of the EAF slag particles are below that size.

MATERIAL AND METHODS

1.0 0.9 0.8

passed amount

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0.001

EAF 1 EAF 2 Ladle

0.01

particle size [mm]

0.1

10

100

Figure 4. Particle size distribution of EAF 1, EAF 2 and ladle slag (Herrmann et al., 2005) Curing, a special feature of materials with cementitious properties occurred after mixing the slags with water. This hardening of the material originates from the hydration reaction and is further explained in Appendix II. Hardening tests described in Herrman et al. (2005) showed that ladle slag hardens very quickly in contrast to EAF slag. In order to be able to use it as a construction material, EAF slag 1 and 2 can be added to decelerate the hardening process that there is at least one day time for construction. Curing of the material originates from hydration which is further explained in chapter 4 of Appendix II. All three types if steel slags, EAF slag 1, 2 and ladle slag, have been categorised as non hazardous waste according to EU legislation (EU, 2002). The mixtures of ladle slag and EAF slag 1 and 2 (in equal shares) used in all measurements are shown in table 2. Table 2. Mixtures of EAF and ladle slag used in the experiments EAF slag [%] Ladle slag [%] 100 0 0 100 35 65 50 50 65 35

MATERIAL AND METHODS

2.2 Methods
In order to quantify the heat release during hydration, the slags are mixed with water and analysed in a calorimeter. The method of IR spectroscopy was taken to observe changes in the chemistry of the hydrated slags, in case of a major part of amorphous minerals in the slags. Furthermore IR spectra are easier to analyse than e.g. X-ray diffractograms. The spectra can be analysed without the use of databases, but identification of a compound is usually not done only with IR analyses. The most certainty is achieved by combining information derived from IR spectra with knowledge of the chemical composition, i.e. other analysis methods. About combinations of IR spectroscopy with other analysis methods has been reported about in Appendix II. In combination with IR spectroscopy, XRD was applied. XRD is especially of use for phase identification of crystalline solids. It is therewith possible to distinguish, e.g. two minerals with the same chemical composition but different crystal structure. The detailed applied methods of IR spectroscopy and XRD are explained in chapter 6 and 7 of Appendix II. Before analyses, the slags were sieved. From EAF slags, the fraction 8 < x > 19 mm and from ladle slag, the fraction < 19 mm was taken and analysed. For the calorimetry measurements, the slag was taken in the original state. Slag samples for IR and XRD analyses were prepared. Each sample was mixed with 10 % of water and compacted in three layers. This water content was determined as optimum water content for a compacted slag mixture with a maximum density. The corresponding Proctorexperiment is found in Herrmann et al. (2005). The specimens were stored in a bucket with 100 % humidity for two days in order to allow hydration of as many minerals as possible during these two days. A complete hydration of the material would take much longer, but not more time than one week of sample preparation was available. After that, the specimens were dried for five days in an exsiccator. It is important that he samples for the IR measurements are dry because otherwise, water would absorb IR radiation and the spectra would be altered. After drying the samples were grinded (particle size required for IR and XRD: < 200 m) and iron particles were removed by a magnet (see also Appendix I for preparation of

MATERIAL AND METHODS

specimens). One ladle slag sample (100%) was analysed with IR spectroscopy without mixing it with water before. Therefore, this sample is called non hydrated ladle slag. 2.2.1 Calorimetry The experiments were carried out with a Parr 1455 Solution Calorimeter. The sample chamber shown in Figure 5 is a fully silvered glass dewar within a stainless steel air can. For isolation the whole assembly is surrounded by a block of plastic foam which lies in a rugged aluminium case. Temperatures are measured with a temperature probe, which has to be immersed to the water in the dewar. The calorimeter is connected to a strip chart recorder. The anticipated temperature range was fixed with the help of the key functions of the calorimeter. The temperature change is simultaneously measured and recorded on a paper sheet. The measurement was cancelled when the temperature decreased up to the initial temperature. The heat outputs of the slags are compared by relating the temperature change to the mass of the slag in the calorimeter. The water in the dewar (ca. 40 ml) and the water later mixed with the sample (water content ca. 30 %) should both have approximately room temperature. The high water content was taken to have an excess of water, because hydration is limited by water content. The water is filled in the measurement assembly before sample addition to record the initial temperature. When the initial temperature is stable, sample is added and mixed with water.

water slag sample in plastic container thermometer water in dewar

Figure 5. Sample cup in the calorimeter

MATERIAL AND METHODS

2.2.2 IR spectroscopy The samples were taken from the same material which has been prepared for the XRD analyses, except of an additional grinding with a mortar before IR analyses. Before measuring the actual samples, a background spectrum needs to be recorded. For this, Potassium bromide (KBr) is used as a so called window material, because it does not absorb in the MID-IR, i.e. it is infrared transparent. To not take up humidity from the air, KBr is stored in an exsiccator. It has to be grinded with a mortar in a bowl as well. The spectrometer automatically subtracts the background spectra of KBr from all measured spectra. The performance of a quantitative analysis was not undertaken. For a quantitative analysis, the analysis has to be performed with a standard included in the sample. 2.2.3 X-ray diffraction For the diffraction experiments, a powder diffractometer was used. A powder diffractometer uses a detector to register the positions of the scattered X-rays. The detector is moved around the sample on a circular plane. Each lattice plane of a crystal in the sample can diffract X-rays at all angles that fulfil the Bragg-equation (see chapter 6.1, Appendix II) and therewith produces a diffraction cone. These diffraction cones consist of very close beams diffracted by crystallites in the powder and are recorded by the detector. Consequently, the received powder diffractogram is determined by the crystal structure and unique for each material.

RESULTS

3 RESULTS
In the following, analyses results of calorimetry, IR spectroscopy and XRD are presented. Further IR spectra are displayed in Appendix I.

3.1 Calorimetry
The heat development of the different slag mixtures is shown in Figure 6 below. The x-axis shows the time, the y-axis the temperature difference per gram slag. The heat released decreases with increasing EAF slag content. For one sample with 100 % EAF slag, the heat development over 60 hours was recorded and it showed a continuous heat release. However, the temperature change was only 0.22 C.
[dT/g] 0.25 0.20 0.15 0.10 0.05 0.00 0 5 10 15 20 25 30 35 time [hrs]
100%LS 35%EAF 50%EAF 65%EAF 100%EAF

Figure 6. Temperature changes per gram slag during hydration measured with calorimetry The diagram shows that the heat development in the dewar occurred under partly adiabatic3 conditions. One part of the released heat of hydration leads to heating of the slag sample, another part is evolved to the environment (depending on isolation properties) and the third part increases the temperature in the calorimeter. At the beginning, conditions are almost adiabatic. Heat generation and heat outflow are in equilibrium at the maximum of the reaction (Zement-Taschenbuch, 2000).

Adiabatic conditions: no heat exchange between sample and environment

RESULTS

3.2 IR spectroscopy
The IR results are compiled in chapter 3 of Appendix I. The IR spectra of EAF and ladle slag plus the spectra of three mixtures of them, i.e. 35 / 50 / 65 % and one additional sample of non hydrated ladle slag were recorded. The IR spectrum of 100 % (hydrated) ladle slag is given as an example in Figure 7. The two below explained peaks A1 and A2 are marked.

0.900 0.85 0.80 0.75 0.70 0.65 0.60 0.55 0.50 K-M 0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.000 4000.0 3000 2000 cm-1 1500 1000 500 400.0 1656 3526 3623 3318 1422 919 929 970 818 476 568 523 866

442 426 411

peak with area A1

peak with area A2

Figure 7. IR spectra of 100 % ladle slag (hydrated sample) The spectrum in Figure 6 is shown in the form wave number vs. Kubelka-Munk units. For qualitative interpretation, just the relation of the peaks is of interest, not the respective Kubelka-Munk value of each peak itself (see chapter 7.4, Appendix II). The range on the x-axis comprises the wave numbers 40,000 to 400 cm-1. In Figure 8, a compilation of all sample spectra is presented.

RESULTS

10

523 983 905 866

590 653 3299

100%EAF, 0% LS

1462 865 978 951

524

653 3526 3338

65%EAF, 35% LS
1660

1418 525

867 817 3528 K-M 1415 1655 867 919 929 972 3527 3622 3328 818 524 669

50%EAF, 50% LS

35%EAF, 65% LS
1655

1418 866 523 919 929 970 1422 1656 818 568

3623

3526

3318

0%EAF, 100% LS

4000

3000

2000 wave number/cm1

1500

1000

500 400

Figure 8. FTIR spectra of two hydrated slags and three hydrated slag mixtures The biggest difference between all spectra is seen in the wave number range from 35003200 cm 1 . The spectrum of hydrated ladle slag shows several peaks, at e.g. 3623 and 3526 cm 1 , whereas the 100 % EAF slag has none there. This wave number range reflects the vibrations of O-H bonds, which can be bound to several components. During the hydration reaction, the water molecules took up spaces in the crystal lattice. If an OH- ion is bound at a different place of the molecule or mineral after reacting with the water, the O-H bond absorbs IR radiation at a slightly different frequency. The mixtures show similar peaks as the ladle slag, but these peaks are not as intense as the ladle slag peak at 1600-1300 cm-1. The latter one is explained further down but the decrease of the ratio between the two peaks is evaluated in Figure 9 below. It shows, that the more ladle slag the sample contains, the more intense is the peak A1 from 37502450 cm-1 compared to peak A2 from 1600-1300 cm-1.

RESULTS

11

6 5 4
A1/A2 35 65

100

3 2 1 0 0 20 40 60 80 100
ladle slag [%] 0

Figure 9. Comparison of area ratio of peaks caused by absorption of OH-bonds A1 = area below the graph from 3750-2450 cm-1 A2 = area below the graph from 1600-1300 cm-1 There is also a broad band around 3200 cm-1 (accompanied with a weak peak at 1655 cm-1), which is caused by physically bound water respectively its asymmetric stretches. That means that water molecules are absorbed to some compound. A general rule is that the lower the wave number, the stronger the bond. The reason is that atoms having a larger mass, e.g. metals, result in higher bond forces and absorb at a lower frequency, i.e. wave number. DRIFTS (Diffuse Reflectance Infrared Fourier Transform spectroscopy) measures the radiation scattered at the surface of a material. Therefore small impacts of the surface, can be seen clearly in the spectrum. But also changes of the air, respectively atmosphere in the sample compartment during the analysis can influence the spectrum. Same spectra, as the one of ladle slag slag show a smaller peak at 2359 cm-1 for example. CO2 is known for having an antisymmetric C=O stretching at 2349 cm-1 (from the rotational spectrum). Probably, the small peak in the steel slag represents the changing CO2 content in the atmosphere during the recording of the KBr as background spectrum and the sample itself. In that so called fingerprint region (from 1500 to 650 cm-1), a spectrum may have hundred or more absorption bands present, but according to Gnzler and Gremlich (2002) only the most intense bands serve as indicators. Therefore, only the most intense peaks can be assigned to a bond. For the other ones, often overlapped by each other, assumptions can be made.

RESULTS

12

A broad band present in all spectra lies at 1500-1350 cm-1, originating from C-O stretching vibrations in the functional group CO3 of inorganic carbonates as CaCO3 (further bands at 880 and 710 cm-1). Also, calcium silicate and calcium aluminate phases are likely to be present. Generally, they show bands from 1100 to 800 cm-1 (CaxSiyOz) as well as from 600 to 500 cm-1 (CaxAlyOz). One problem of analysing them with certainty is that many bounds show absorption in that area. Resolving the broad (overlapping) bands of spectra is complicated. However, the 970 cm-1 is considered to be originated from calcium silicate phases as this peak can be seen rather clearly. The stretching vibration of the Si-O bond in calcium silicates absorbs in the region 1100-800 cm-1 as well as from 600 to 500 cm-1. Anhydrous calcium silicates anhydrous refers to no crystalline water absorb at 920 cm-1, 536-526 and 464-458 cm-1 (Gomes and Ferreira, 2005). Furthermore, they are known for having puzzolanic properties. Hydrated ladle slag shows the 920 cm-1 band. But with an increasing amount of EAF, this peak is getting harder to identify. Because oxides of iron, aluminium and small amounts of magnesium are present in the slags, those are worth to look for as well. Al-O stretching vibrations occur in the region from 950-800 cm-1 and the strong peak at 866 cm-1 in the ladle slag spectrum is probably due to Al-O stretching vibration. This peak is shifted towards 860 cm-1 in the non hydrated ladle slag and also present at the 100 % EAF slag samples, but with much lower intensity. The aluminium peak is much weaker in the EAF spectra, because ladle slag has a three times higher aluminium content than EAF slag. Possible compounds containing aluminium can be calcium alumino silicate hydrates (C-A-S-H). Speaking about differences in the spectra, it can be said, that the relation of the peak around 866 cm-1 and the peak around 970 cm-1 changes with EAF content. The more EAF the sample contains, the higher is the intensity of the around 970 cm-1 compared to the peak around 866 cm-1. As said before, the first peak is assumed to be aluminium while the second is related to calcium silicates. Another peak shifting between hydrated and non hydrated ladle slag has occurred from 568-576 cm-1. Possible compounds causing these bands are again aluminium or iron oxides (610-520 cm-1 and 580-560 cm-1), whereas magnesium oxide bands should be

RESULTS

13

placed at slightly lower wave numbers (~560-550 cm-1). But calcium silicates and aluminates absorb in this range as well. Molecules absorbing at wave numbers lower than 700 cm-1 cannot be identified with certainty.

3.3 X-ray diffraction


Steel slags are a very complex material, which means they can contain a variety of minerals. The XRD measurements showed that most of the minerals are present as crystals, i.e. very few amorphous phases have been detected. The presence of amorphous structures can be detected with XRD as an increase of the baseline from 2 (2-Theta) = 20 on. But the pattern produced of an amorphous phase cannot be assigned to a compound. For identification, the diffractogram is compared with minerals in a database. If a sample consists of more than one mineral, as it is the case for steel slags, the different peaks of each substance overlap each other and get harder to identify. A mineral only can be detected if the sample contains more than 4 % of it. EAF slag and ladle slag consist of different minerals. In Figure 10, the diffraction pattern of 100 % ladle slag and 100 % EAF slag are shown.
X-ray diffraction pattern of steelslags

100 % ladle slag

Intensity

100 % EAF 100 % Ladle

100 % EAF slag

10

20

30

40

50 2 - Theta - Scale

60

70

80

90

Figure 10. Diffraction pattern of 100 % ladle slag and 100 % EAF slag

RESULTS

14

The mixtures of EAF and ladle slag only contained mixtures of the minerals of both samples indicating that no new minerals have been formed. The minerals detected have been: Ladle slag Periclase Dicalcium silicate Iron Spinel Mayenite Dicalcium Silicate MgO

- Ca2SiO4
Fe MgAl2O4 Ca12Al14O33

- Ca2SiO4

EAF slag Iron Merwinite Monticellite Clinoenstatite Dicalcium Silicate Magnesium Aluminium Oxide Fe Ca3Mg(SiO4)2 CaMgSiO4 MgSiO3 Ca2SiO4 MgAl2O4

Out of these, the main minerals were

- Dicalcium silicate ( - Ca2SiO4) and Mayenite in ladle slag and


Merwinite and Monticellite in EAF slag.

The minerals have different properties considering their hydraulic behaviour. Periclase for example forms hydraulic minerals under addition of water. In XRD analysis, the peaks of high intensity can be assigned to a certain mineral. The strong peak in the EAF slag diffractogram for example originates from periclase. Furthermore, different phases of dicalcium silicate have been recorded. They are formed during cooling of the molten slag. Each of the five polymorphs of Calcium silicate has a different crystal structure and different properties.

DISCUSSION

15

4 DISCUSSION
Method development for preparing sample specimens For the IR and XRD analyses, a method of sample preparation including hydration of slags and compaction was developed. Five different slag specimens according to five mixtures were prepared. They were stored in a 100 % humid atmosphere for two days (see description in chapter 2 of Appendix I). This short period of time restricts the curing processes since the hydration is limited by the water content. If water is available, the hydration will continue until all silica molecules have reacted with the OH- ions. The short curing time affected certainly the results of the mineralogical analyses but the time for preparing samples was limited by external circumstances and, also, the study had a survey character, i.e. the results are considered sufficient for a first overview and more investigations are planned. Analysis methods The common area for the application of IR spectroscopy is analysis of the chemical structure of organic compounds. However, no reason could be identified - by studying the literature (Appendix II) - to not use IR spectroscopy for inorganic compounds as well. Furthermore, the possible presence of a considerable amount of amorphous material in the slags suggested the IR method. The evaluation of the IR spectra of steel slags was based on personal experience and literature data. However, available databases for IR data were difficult to use because steel slags are very complex and contain a broad variety of minerals. Absorption data from databases mostly refer to pure chemical compounds. IR measurements of such complex materials as steel slags can not give evidence for the presence of a compound with absolute certainty. Together with the knowledge of the chemical composition and the absorption data, it only allows statement s like that the present elements and functional groups absorb in a certain wave number range. If absorption in that wave number range was measured, it can originate from the assumed compound, but it also can originate from the absorption of other compounds or influences as sample preparation or changing conditions while the analyses were performed. A quantitative analysis has not been performed. In such an analysis a standard is measured together with the window material (KBr) and the slag.

DISCUSSION

16

The analyses of hydrated and non hydrated ladle slag proved the integration of hydration water in the slag structure. The absorption bands below 1000 cm-1 and particularly below 700 cm-1 are difficult to assign to a chemical compound as not only carbonates, calcium silicates and calcium aluminates absorb in that range but also iron, aluminium and magnesium compounds. The differentiation of mineral phases as calcium silicates as tricalcium silicate and dicalcium silicate is not possible with IR measurements. Furthermore, conditions in the atmosphere of the sample compartment in the apparatus, as for example CO2 and air humidity can have an influence on the measurements. This is because water vapour and carbon dioxide absorb in the MIR. If the atmospheric conditions in the sample compartment are the same during the analysis of both the sample and the background, the instrument will ratio out these bands and they are not seen anymore in the final spectra (Smith, 1996). The IR spectrometer had to be moved to another room between the first experiments (including measurement of background) and the repeated analyses of 50 % EAF slag and non hydrated ladle slag. However, only a little disturbance around 2350 cm-1 has been caused by this. The investigation of the crystal structures was done by XRD analyses. Even if it is not possible to identify amorphous phases with XRD, the diffractogram of a sample containing amorphous phases shows a hump of the background in the range 2 (2 Theta) ~ 20 to 40. In the diffractograms, this hump was very low. Hence, the majority of the minerals in the slags are present in a crystalline state. The time for crystallisation after tapping of the slag is determined by the slag treatment. The Uddeholm slags have been stored and cooled by air contact and could therefore crystallise during storage. As diffraction occurs at the sample surface, the diffracted X-rays only contain information about the minerals detected at the surface. For that reason the sample preparation has to be very careful, so that crystals are evenly distributed in the sample. The information about the main minerals in the EAF slag and ladle slag was attained by thermo dynamic calculations. The diffractograms were evaluated by a database. Except of some very intensive, clear peaks, it is impossible to analyse them visually, because of the number of peaks caused by each mineral. XRD as well as IR peaks can overlap each

DISCUSSION

17

other, the peaks can be shifted on the x-axis or they can differ in intensity from sample to sample. Some compounds have very similar diffraction patterns. They can consist of the same crystalline phase but include different irregularities in their crystal structure. This phenomenon is called solid solution. Under certain conditions, minerals can exchange atoms. For example calcium silicate phases as Ca(Mn)Si2O6 can have iron atoms at some places in the crystal structure. XRD is not able to detect those small differences at the atomic level. XRD analyses further proved that no mineral formations were induced by mixing EAF and ladle slag. Only minerals that were present in the pure slags could be detected in the mixtures. One possible explanation is that no new phases have been formed (at the present conditions, e.g. 25 C), but it is also possible, that new formed phases were below the detection limit of 4 wt-%. As only the surface is scanned by X-rays, small varieties of the particle distribution originating from the sample preparation could cause errors too. Heat generation and curing behaviour The curing properties and the released heat of hydration have been analysed with the calorimeter. The heat generation was highest for pure ladle slag while pure EAF slag released no or very little heat. The ladle slag specimen hardened very fast and, looking at the different mixtures, curing was the faster the higher the portions of ladle slag. Ladle slag has a CaO/SiO2 ratio of 3 and hence, is considered as a hydraulic material. The larger this ratio, the higher is the hydraulic reactivity of the material. Even if aluminate activates the hydration and the formation of cement phases, the maximum heat output occurred slightly later, the more ladle slag, i.e. aluminate, the sample contained. The hydration reaction of pure ladle slag occurs 5 hours later compared to the mixture containing 65 % EAF slag. Probably, the presence of a cement activator can retard the time of maximum heat release. The function of aluminate in the mixtures of EAF and ladle slag was weak not just because of a lower amount of ladle slag but also because of the low amount of reactive

DISCUSSION

18

lime and high silica in EAF slag4 (see composition in chapter 2). That means that EAF slag of that composition can be seen as a latent hydraulic material even though almost no heat output has been recorded. From cementitious materials it is known that a slow curing process with heat output over longer period leads to higher long-term stability. For answering the question, whether the reaction of the samples containing EAF slag proceeds faster but stops earlier, or if the low reaction rate leads to a continuous reaction, longer measurements would be needed. Strength and stability of phases Although ladle slag released the most heat of hydration, it is not sure that the sample develops the highest final strength during curing. The strength developing characteristics depend primarily on the mineral phases: they contribute either to early strength (e.g. tricalcium silicate) due to higher heat of hydration or to later strength (e.g. dicalcium silicate) due to less heat of hydration (Dobrowolski, 1998). It has been observed during sample handling that the cured specimen consisting of 100 % ladle slag collapsed when touched after three months. It had been stored in a room together with the other samples. As the sample with 100 % EAF slag did not cure, it had not formed a stable specimen after hydration. All specimens consisting of slag mixtures were still stable after three months. The alumina content of ladle slag of 23 wt-% is compared to EAF slag relatively high. The instability of the ladle slag specimen asserts the hypothesis of very low final strength of cementitious materials containing high aluminate (see Appendix II, chapter 4.1). Aluminous cement shows a (compared to OPC) fast and intensive hydration reaction with monocalcium aluminate being the main mineral phase. Low final strength of aluminous cement is caused by mineral transformations of monocalcium aluminate during curing. The minerals developed at the end of the hydration reaction (e.g. dicalcium aluminate hydrate) have a different crystal structure and are less stable than

CaO/SiO2 ratio EAF slag = 0.9

DISCUSSION

19

monocalcium aluminate. The same hydration products could have been formed in ladle slag and instead of reacting with silicates, calcium could have reacted with aluminate, which in the following could have caused low final strength. Another possible reason for the disintegration of the ladle slag specimen could be the expansion of mineral phases. As been detected with XRD analyses, a substantial amount of periclase is present in ladle slag. Periclase is known for expansion after hydration. Also, the phase - Dicalcium silicate ( -Ca2SiO4) was measured. This phase is formed of - Ca2SiO4 during cooling of the molten slag. The different phases of dicalcium silicate all have a different crystal structure. During phase transformation, the change in the crystal structure leads to a disintegration of the mineral. This also can be a reason for the fine structure of ladle slag. However, no complete explanation of the observation can be provided. Mineral alterations Even though no long-term behaviour has been measured in this study, some additional observations after three months of storage could be made. The colour of the three months old specimens was lighter than directly after the preparation which could be caused by carbonation and calcite formation on the surface. The formation of carbonates and hence the development of a high buffer capacity is one assumption for mineral alterations in a liner consisting of steel slags. The mineral alterations that are estimated for slags consisting of calcium silicates and calcium aluminates also include the formation of C-S-H and C-A-H phases. These phases have a good adsorption capacity for heavy metals due to their large reaction surface (see Appendix II, chapter 4.3). Other types of so called cash minerals that could hinder the release of contaminants are iron and aluminium phosphates/hydrates/hydroxides and silicates. It is hard to draw conclusion from literature data of ashes and slags regarding mineral alterations. How much of a material will be transformed and which secondary phases are developed, has to be investigated for each type of material separately. Ashes and slags can differ very much in their composition which is reflected also in the literature where considerable variations of data for mineral alterations of MSWI ashes are reported.

DISCUSSION

20

Application of steel slags in a liner As ladle slag adds the reactive compounds to a mixture and addition of EAF slag leads to higher long-term stability, both slag types have their own function and are necessary in construction applications. The 50/50 mixture is most favoured in a liner application because its hydraulic behaviour, curing time and stability showed to be the best for the target function. Principally, the chemical and mineralogical composition encourages the application of steel slags in a top cover construction of a landfill. Through compaction, an increase in buffer capacity will be achieved, as gas and water fluxes need more time to reach the reactive surface of the material. Furthermore, construction materials containing carbonates have advantages considering the expected chemical and mineralogical changes. Future experiments Further analyses with regard to the stability of mineral phases, the formation of secondary mineral phases and the long time behaviour need to be done. Humidity and carbon dioxide influence these mineral alterations. Hypotheses about possible secondary mineral phases have been outlined in the literature review. The expansion of free CaO and MgO due to late hydration is one problem of applying steel slags as a construction material. If a construction material does not have sufficient volume stability, the stability of the whole construction is endangered. If longer measurements will be performed, much more efforts are necessary. A bigger number of specimens (including parallels) has to be stored under defined conditions, e.g. fixed CO2 content and humidity, and more IR and XRD measurements have to be performed after different periods of sample storage. There are good reasons to assume that the described mineral alterations can be detected with these two analyses methods. Quantitative IR as well as XRD measurements should be considered. If possible, the quantitative methods should be favoured. Suggested time spans for sample storage are 30 days, half a year and one year. Furthermore, SEM analyses could complete the picture about the mineralogical slag structure as phases below 4 wt-% and non crystalline material cannot be measured with XRD. The presence of crystalline structures could be unveiled by this type of

DISCUSSION

21

microscopy. One could illustrate the topography of the surface. Simultaneously, data of the crystal units are measured. Models estimating the time for decomposition of ash layers consisting of carbonates by carbonation result often in time spans of thousands of years (Ecke, 2003). Results of models performed with steel slag compositions, layer thickness and climate data would be interesting. Also, further investigations about the stability of the estimated secondary phases under landfill conditions are necessary. At present thermo dynamical data and secondary mineral phases are not available for all of the measured minerals.

CONCLUSIONS

22

5 CONCLUSIONS
Calorimetry, IR spectroscopy, XRD as well as sample handling and experiences with preparing slag specimens provided the following findings. In Europe steel slags are often landfilled or temporarily stored, although applications for their reuse already exist (e.g. as additives in a road construction). The target of nowadays research is to identify further applications for reusing steel slags and to investigate the environmental impact that steel slags would have. The conditions present in the liner have to be estimated before using alternative construction materials as steel slags. Up to today, the long-term behaviour is still unknown. It is affected by processes as weathering, including carbonation (carbonic acid weathering) and pH changes, leaching, aging of mineral phases and therewith stability changes of the minerals. XRD and IR spectroscopy are suitable methods to analyse the mineral phases of steel slags. The reaction of the slags under addition of water is called hydration which has been described in this literature review. To determine the heat development and conditions of this reaction, calorimetry is a suitable technique. Ladle slag releases the most heat during hydration, while the heat release of EAF slag is very little. The maximum heat output occurred the later the more ladle slag was in the mixture. The ladle slag specimen cured fastest. The EAF slag sample was not curing to a rock-like compound and developed no mechanical strength. A conclusion regarding the correlation of curing behaviour and mineral phases formed is possible in the way that a high amount of certain mineral phases as dicalcium silicates results in limited cementitious properties. Such mineral phases have been recorded by XRD in both slag types.

CONCLUSIONS

23

The heat release during hydration does not necessarily correlate to the stability of the hydration products, i.e. there is no correlation between heat of hydration and developed final strength.

Ladle slag showed a higher reactivity than EAF slag, but probably has a lower final strength, which is concluded from the high alumina content and the properties of similar cement types. However, the investigation of the final strength after curing was not part of the measurements.

A mixture of EAF slag and ladle slag is recommended for a landfill cover. A sample preparation method was developed for mineral analyses, which worked well and can be applied in further tests. With this method explained in Appendix I the mineral phases after hydration could be measured by IR and XRD analyses.

IR spectroscopy revealed the different chemical bonds and compounds formed after hydration. The IR spectra and the intensities of the peaks changed proportional to the ladle slag content in the mixture. For example, the detection of hydrated water was the lower; the more ladle slag was present.

Both steel slags consist predominantly of crystalline phases. It is likely that solid solutions are formed during slag cooling. However, these irregularities of the crystalline phases cannot be detected with XRD. According to the XRD analyses, no new minerals have been formed after mixing the two steel slag types.

Further research Slag storage and how slag properties change with different storage methods or slag treatments should be investigated more detailed. The stability of mineral phases present in steel slags, e.g. merwinite, monticellite, mayenite and phases consisting of calcium silicate, ferrite, magnesia and aluminate is mainly influenced by humidity, carbon dioxide and pH changes. Humidity and carbonation are assumed to be correlated but this has not been analysed for steel slags up to now.

CONCLUSIONS

24

Secondary mineral phases of the analysed phases are assumed to be carbonates and bicarbonates. The formation of carbonates will be a short-term process, while bicarbonates are formed over very long time periods (in the range of thousands of years). The amount of minerals that will react and be transformed into secondary phases is unknown. Compaction will increase the buffer capacity and contribute to longer reaction times. More knowledge of stability and long-term behaviour of mineral phases of steel slags can be achieved with long-term experiments and by modelling and further thermo dynamical data about the analysed minerals.

REFERENCES

25

6 REFERENCES
Andreas, L., Herrmann, I.; Lidstrom-Larsson, M.; Lagerkvist, A. (2005). Physical properties of steel slag to be reused in a landfill cover, Sardinia 2005, Tenth International Waste Management and Landfill Symposium, S. Margherita di Pula, Cagliari, Italy; 3-7 October 2005. Dobrowolski, J. A. (1998). Concrete Construction Handbook. 4th ed., Mc Graw-Hill Inc., New York, p.1.15, 1.17 et seq. Ecke, H. (2003). Sequestration of metals carbonated in municipal solid waste incineration (MSWI) fly ash. Waste management vol. 23, p. 631- 640. EU (2002). "Council Decision establishing criteria and procedures for the acceptance of waste at landfills pursuant to Article 16 and Annex II of Directive 1999/31/EC." Document 14473 ENV 682.Council of the European Union, Brussels. Fllman, A-M. (1997). Charaterisation of Residues Release of contaminants from slags and ashes. Doctoral Thesis Linkping University, Sweden, p. 9. Gadsden, J. A. (1975). Infrared Spectra of Minerals and Related Inorganic Compounds. London, Butterworth, p. 6et seq., 23et seq., 62. Gomes, C. E. M.; Ferreira, O. P. (2005). Analyses of Microstructural Properties of VA/VeoVA Copolymer Modified Cement Pastes. Polmeros: Cincia e Tecnologia, vol. 15, n 3, p. 193-198. Gnzler, H.; Gremlich, H-U. (2002). IR Spectroscopy - An Introduction. WILEY-VCH Verlag GmbH, Weinheim, Germany, p. 176.

REFERENCES

26

Herrmann, I.; Lidstrm Larsson, M.; Andreas, L. (2005). Anvndning av stalslagg i sluttckningen av Hagfors kommunala deponin. Delrapport, MIMER, Lule Tekniska Universitet, Sweden. Hirschmann, G. (1999). Langzeitverhalten von Schlacken aus der thermischen Behandlung von Siedlungsabfllen. Fortschr. Ber. VDI Reihe 15 Nr. 220. VDI Verlag, Dsseldorf, p. 153. IUPAC (1997). Compendium of Chemical Terminology. 2nd Edition. Blackwell Science. International Union of Pure and Applied Chemistry IUPAC. Online version of IUPAC compendium: http://www.chemsoc.org/cgi-shell/empower.exe?DB=goldbook Knoblauch, H.; Schneider, U. (1992). Bauchemie. Werner-Verlag GmbH, Dsseldorf, p. 126, 160. Krenkler, K. (1980). Chemie des Bauwesens. Band 1: Anorganische Chemie. SpringerVerlag, Berlin, Heidelberg, p. 405. Motz, H. and Geiseler, J. (2001). Products of steel slags as an opportunity to save natural resources. Waste Management, Vol. 21, p. 285-293. Shen, H. et al. (2004). Physicochemical and minerological properties of stainless steel slags oriented to metal recovery. Resources, Conservation and Recycling 40, p.245-271. Shi, C. (2002). Characteristics and cementitious properties of ladle slag fines from steel production. Cement and Concrete Research vol. 32, p. 459-462. Smith, B. C. (1996). Fundamentals of Fourier transform infrared spectroscopy. CRC Press LLC, Boca Raton, Florida, USA, p. 30. Zement-Taschenbuch (2000). Verein Deutscher Zementwerke e.V. (ed.). 49th ed. Verlag Bau+Technik GmbH, Dsseldorf, Germany, p. 322.

APPENDIX I

APPENDIX I

SAMPLE PREPARATION AND MEASUREMENT DATA

1 CALORIMETRY ....................................................................................... 2 2 PREPARATIONS OF SPECIMENS FOR IR SPECTROSCOPY AND XRD EXPERIMENTS.................................................................................. 4


2.1 Sample preparation............................................................................................ 4 2.2 Storage of specimens and grinding.................................................................... 6 2.3 Observations ...................................................................................................... 7

3 IR SPECTROSCOPY ................................................................................ 7 4 X-RAY DIFFRACTION.......................................................................... 10 5 REFERENCES......................................................................................... 12

APPENDIX I

1 CALORIMETRY
The EAF slag was already crushed to a size smaller than 20 mm at Uddeholm Tooling AB. Sieving at 20 mm for ladle slag was planned, but a 20 mm sieve was not available at the university laboratory. That is why EAF 1, EAF 2 and ladle slag (sample no. 5) were sieved with a 19 mm sieve to remove the fraction > 19 mm. Furthermore, the fraction < 8 mm of EAF slag 1 and 2 was removed by sieving. Each slag type was homogenised and reduced. EAF slag 1 and 2 were mixed in equal shares to form the EAF fraction. These slag fractions were used for all performed measurements. The exact data of the mixtures measured in the calorimeter are presented in table 1. Table 1. Sample data EAF fraction in [%] mass EAF slag in [g] mass ladle slag in [g] mass of water in plastic container in [g] mass of water in dewar in [g] 0 (ladle slag) 30.04 10.27 40.66 35 10.44 19.48 10.04 40.11 50 15.75 15.72 10.47 40.52 65 19.54 10.54 10.57 40.10 100 30.32 10.52 40.22

The recorded values measured by the calorimeter for each sample are presented in table 2 to 6. Table 2. Recorded data of 100 % ladle slag sample time T dT dT/g slag [hrs] [C] [C] [C/g] 0 5 10 15 20 21 25 30 35 21.25 22.95 23.35 24.75 27.35 27.4 26.43 24.92 23.65 0 1.70 2.10 3.50 6.10 6.15 5.18 3.67 2.40 0.00 0.06 0.07 0.12 0.20 0.20 0.17 0.12 0.08

APPENDIX I

Table 3. Recorded data of 35 % EAF slag sample time T dT dT/g slag [hrs] [C] [C] [C/g] 0 2.5 5 7.5 10 15 20 25 30 35 22.94 23.35 23.94 24.2 24.3 25.25 26.68 26.08 24.95 24.05 0 0.41 1.00 1.26 1.36 2.31 3.74 3.14 2.01 1.11 0 0.01 0.03 0.04 0.05 0.08 0.13 0.10 0.07 0.04

Table 4. Recorded data of 50 % EAF slag sample time T dT dT/g slag [hrs] [C] [C] [C/g] 0 5 10 15 17.5 20 25 30 35 21.98 22.83 23.00 24.74 25.24 25.00 24.07 23.17 22.58 0 0.85 1.02 2.76 3.26 3.02 2.09 1.19 0.60 0.00 0.03 0.03 0.09 0.10 0.10 0.07 0.04 0.02

Table 5. Recorded data of 65 % EAF slag sample time T dT dT/g slag [hrs] [C] [C] [C/g] 0 5 10 15 20 25 30 35 21.88 22.65 23.23 24.19 23.80 23.07 22.80 22.55 0.00 0.77 1.35 2.31 1.92 1.19 0.92 0.67 0.00 0.03 0.04 0.08 0.06 0.04 0.03 0.02

APPENDIX I

Table 6. Recorded data of 100 % EAF slag sample time T dT dT/g slag [hrs] [C] [C] [C/g] 0 5 10 15 20 25 30 35 21.45 21.72 21.68 21.64 21.93 22.12 21.90 21.70 0.00 0.27 0.23 0.19 0.48 0.67 0.45 0.25 0.00 0.01 0.01 0.01 0.02 0.02 0.01 0.01

2 PREPARATIONS OF SPECIMENS FOR IR SPECTROSCOPY AND XRD EXPERIMENTS


Specimens for IR and XRD analyses had to be prepared in order to detect the chemical and mineral structure of the hydrated samples. The used spectroscopic method was the DRIFTS method which cannot be applied for wet samples, because the water absorbs radiation and the spectra would be altered.

2.1 Sample preparation


The sieving of the original slag fractions has been explained above (see chapter 1, Appendix I). They were further used for preparation of specimens. The different mixtures shown in table 7 were formed and the corresponding mass of each sample fraction was recorded. The mass of EAF and ladle slag needed for e.g. the specimen consisting of the 100 % mixture differed because the density of EAF slag is less than for ladle slag. The height of all specimens was about 4.7 cm.

APPENDIX I

Table 7. Mixtures for preparation of specimens sample no. fraction of EAF slag in [%] 1 2 3 4 5 0 35 50 65 100 mass of EAF slag in [g] 63.85 78.86 117.14 198.54 mass of ladle slag in [g] 144.32 117.51 78.86 63.44 mass of water in [g] 14.43 19.43 16.18 18.18 16.15

Each slag sample was separated in three equal parts, mixed with about one third of the corresponding amount of water and compacted. The necessary knocks of one layer with the proctor device were calculated according to the following. Calculation The sample compaction was carried out according to SS 02 71 09 (SIS, 1994) except that a different proctor device (than the standard proctor device) was used. The number of beats from the proctor device was calculated according to equation 1 below in order to compact the samples with a certain energy. The energy applied was assumed to be 2.5 Nm/cm3 (according to SS 0271 09). Table 8. Data of the cylinder height height of sample diameter sample volume [cm] [cm] [cm] [cm3] 9.0 4.7 5.0 92.28

Table 9. Data of modified Proctor device height falling weight diameter of knock area energy applied [m] [kg] [cm] 0.295 2.099 3.0 2.5

[Nm/cm3]

APPENDIX I

The following formula was used to calculate the necessary knocks with the proctor device for the requested energy input of 2.5 Nm/cm3. Equation 1 for calculating energy input with proctor devise: n1 number of slag layers in specimen number of knocks with proctor devise mass of falling weight at Proctor devise[kg] acceleration due to gravity [m/s2)] height of falling weight before compaction [m] sample volume [cm3] applied energy [Nm/cm3]

n1 * n2 * m * g * h =E V

n2 m g h V E

Before getting the necessary knocks for obtaining the stated energy input, unit conversion was done. The result was again multiplied with a factor of 0.82, because the relation of cylinder diameter to diameter of knock area of the standard proctor device (102mm/50mm) in SS 02 71 09 is bigger than the one of the used proctor devise (50mm/30mm). Therefore 12.6 * 0.82 10 knocks with the bearable proctor device had to be applied for specimen compaction.

2.2 Storage of specimens and grinding


The specimens were stored in a bucket with 100 % humidity to allow a full hydration reaction over this time. However, the reaction will not continue if there is no humid atmosphere. For a longer hydration reaction, a longer storage time with 100 % humidity must be taken. For these measurements, not more time than one week of sample preparation was available. After two days in the bucket, the specimens were put in an exsiccator. This was done because the sample material for the IR measurements had to be dry. After, five days of curing in the exsiccator, the specimens were taken out. One day before X-ray measurements, the specimens were pulverized. At first, some material was scratched off the specimen with big pliers. This material was put in a grinding apparatus. Before starting the grinding process, a magnet was held over the

APPENDIX I

sample and small iron particles were taken out. Then grinding started. It was also possible to look inside the apparatus and adjust the grinder. Between several grinding steps, the apparatus was opened and the magnetic fraction was removed again. Otherwise, these particles could disturb the analyses. After grinding, the sample was put in a little plastic bag.

2.3 Observations
It was observed from earlier compaction experiments that the 100 % EAF slag specimen had a crumble consistency after curing. The specimens containing both EAF and ladle slag exhibited higher strength after standing in room conditions for three months. The 100 % ladle slag specimen became less stable over this time. This indicates that EAF is basically stabilizing the whole structure, e.g. as aggregate in cement. However, no strength measurements were performed.

3 IR SPECTROSCOPY
The five slag samples were grinded with a mortar in a bowl a second time. The non hydrated ladle slag and the KBr, which was used as a background material, were grinded in that way as well. For the measurements, the samples were diluted in KBr (3.5 % of sample). The material was weighed and mixed with the KBr by using a little piece of paper. The material is diluted because only a small sample amount (in the range of some mg) is needed. A particle size of 2 m (Gadsden, 1975) is to be preferred. Afterwards, the KBr and the slag sample are carefully put in the sample cup. As for the XRD measurements as well, shaking or pressing of material has to be avoided. Instead, a small spatula is pushed over the plane of the sample cup. If no even surface was obtained, the sample cup has to be filled again. The sample cup (filled with about 20 to 25 mg of material) is than put in the specimen holder and the data (e.g. sample name, scanning range) are given into the computer. Before starting the measurement, waiting of five minutes was necessary to have stable atmosphere conditions in the sample compartment. The measurement itself included 130 scans of the sample and took about 20 minutes. After each measurement, the sample cup was cleaned with cotton wool.

APPENDIX I

The spectra of the five hydrated slag samples is shown in Fig. 1, whereas the comparison between hydrated and non hydrated ladle slag performed by IR spectroscopy is shown in Figure 2.

523 983 905 866

590 653 3299

100%EAF, 0% LS

1462 865 978 951

524

653 3526 3338

65%EAF, 35% LS
1660

1418 525

867 817 3528 K-M 1415 1655 867 919 929 972 3527 3622 3328 818 524 669

50%EAF, 50% LS

35%EAF, 65% LS
1655

1418 866 523 919 929 970 818 568

3623

3526

3318

0%EAF, 100% LS
1656

1422

4000

3000

2000 wave number/cm-1

1500

1000

500 400

Figure 1. IR spectra for all hydrated slag samples (LS = ladle slag)

APPENDIX I

866

523

568 476

919 929 970

818

860

K-M 3526 3623 3318

818

473 492 521 576

hydrated ladle slag


1656

1422

919 928 973

3300

non hydrated ladle slag


3000 2000

1459

4000

1500

1000

500 400

Figure 2. IR spectra for hydrated ladle slag and non hydrated ladle slag

523 983 905 866

590 653

100%EAF, 0% LS
3299 1462 866 523 919 K-M 970 929 818 568

3526 3623 3318

0%EAF, 100% LS
1656

1422

4000

3000

2000

wave number/cm-1

1500

1000

500 400

Figure 3. IR spectra of 100 % EAF slag and 100 % ladle slag (hydrated)

APPENDIX I

10

4 X-RAY DIFFRACTION
For X ray diffraction analysis just a small amount of the solid sample is needed. Before putting the sample in the diffractometer, the sample was put in a small round deepening of a thin plastic plate. The difficulty is to have an even sample surface but not to press or shake the material in the plate. This would change the result, because the premise of the analysis is that the crystals are randomly orientated over the surface. The flat plate with the sample is than put on the circumference of an X-ray focusing circle. One analysis took approximately 1.5 hours.
X-ray diffraction pattern of steelslags

100 % ladle slag

Intensity

100 % EAF 100 % Ladle

100 % EAF slag

10

20

30

40

50 2 - Theta - Scale

60

70

80

90

Figure 4. Diffraction pattern of 100 % ladle slag and 100 % EAF slag

11

Table 10. Main IR peaks of 100 % EAF slag, 50 % EAF slag and the two ladle slag samples including literature data
slag type and date of measurement (nh = non hydrated) 100%EAF (12.12.) 100%EAF (21.12.) 50%EAF (21.12.) 100%LS (12.12.) 100%LS_nh (21.12.) 100%EAF 100%EAF 50%EAF 100%LS 100%LS_nh 100%EAF 100%EAF 50%EAF 100%LS 100%LS_nh (12.12.) (21.12.) (21.12.) (12.12.) (21.12.) (12.12.) (21.12.) (21.12.) (12.12.) (21.12.) wave number Literature [cmauthor corresponding vibration Silanol SiO-H stretch O-H stretches possible compounds

3300 3468 3528 3526 3300 1458 1459 1415 1422 1459 982 983 867 866 860

3500-3400 ~3440 3700-3200 3440-3446 (ancl.16401436-1424 1510-1410 ~1463 1520-1320

Smith (1999)

Gomes and Ferreira (2005)

silica (Si-OH bonds) combined and adsorbed water of C-S-H and aluminate phases

Gomes and Ferreira (2005) Smith (1999) Smith (1999) Gnzler and Williams (2001)

C-O stretch C-O stretch antisymm. CO3 stretching vibrat.

carbonate phases inorganic carbonates carbonate in inorganic salts

880 + 710 874-880 and 920 880-860 920-800 986-970 ~940 ~805 536-526

Gomes and Ferreira (2005) Gomes and Ferreira (2005) Gomes and Ferreira (2005) Smith (1999) Socrates (1994) Gomes and Ferreira (2005) Smith (1999) Smith (1999) Gomes and Ferreira (2005)

C-O stretch C-O stretch C-O out of plane bend AlO2silanol Si-O stretch Si-O-Si symm. stretch

carbonate phases anhydrous calcium silicates inorganic carbonates Al-ion (also 670-620, etc) calcium silicates silica

100%EAF 100%EAF 50%EAF 100%LS 100%LS_nh

(12.12.) (21.12.) (21.12.) (12.12.) (21.12.)

521 522 525 523 521

anhydrous calcium silicates

APPENDIX I

12

5 REFERENCES
Dobrowolski, J. A. (1998). Concrete Construction Handbook. 4th ed., Mc Graw-Hill, Inc., p. 1.15. Gomes, C. E. M.; Ferreira, O. P. (2005). Analyses of Microstructural Properties of VA/VeoVA Copolymer Modified Cement Pastes. Polmeros: Cincia e Tecnologia, vol. 15, n 3, p. 193-198. Gnzler, H.; Williams, A. (2001). Handbook of Analytical Techniques. Vol.1. WILEYVCH Verlag, Weinheim, Germany, p. 471 Socrates, G. (1994). Infrared characteristic group frequencies. 2nd ed. Smith, B. C. (1999). Infrared Spectral Interpretation - A systematic approach. CRC Press LLC, Boca Raton, Florida, USA, p. 165 Svensk Standard SS 02 71 09, 1994. Geotekniska provningsmetoder Kornfrdelning Siktning. SIS Standardiseringskommisionen i Sverige.

APPENDIX II

APPENDIX II

STEEL SLAGS GENERAL DATA, MINERALOGICAL COMPOSITION AND SUITABLE ANALYSIS METHODS FOR DETERMINING HEAT OF HYDRATION AND MINERAL PHASES LITERATURE REVIEW

APPENDIX II

II

TABLE OF CONTENTS

1 INTRODUCTION...................................................................................... 1 2 ORIGINS AND FORMATION OF ELECTRIC ARC FURNACE AND LADLE SLAG .............................................................................................. 2
2.1 Electric Arc Furnace slag (EAF-slag) ............................................................... 2 2.2 Ladle slag........................................................................................................... 2

3 REUSE OF STEEL SLAGS ...................................................................... 3


3.1 Generation and utilisation of steel slags in Europe ........................................... 5 3.2 Utilisation of steel slags in a landfill cover construction .................................. 8

4 MINERAL PHASES................................................................................ 10
4.1 Mineral phases of cement................................................................................ 11 4.2 Mineral phases of steel slags ........................................................................... 20 4. 3 Alteration of mineral phases........................................................................... 24

5 CALORIMETRY ..................................................................................... 29 6 X-RAY DIFFRACTION.......................................................................... 31


6.1 Physical background and sample preparation ................................................. 32 6.2 Interpretation of one X-ray diffractogram of steel slag................................... 33

7 IR SPECTROSCOPY .............................................................................. 34
7.1 Physical background of Vibrational Spectroscopy.......................................... 35 7.2 Technique of the FTIR Spectrometer .............................................................. 39 7.3 The DRIFTS method ....................................................................................... 40 7.4 Interpretation of IR spectra.............................................................................. 41

8 DISCUSSION .......................................................................................... 44 9 CONCLUSIONS...................................................................................... 47 10 LITERATURE CITED .......................................................................... 48

APPENDIX II

1 INTRODUCTION
Many landfills in Europe have to be closed due to the regulations in the EU landfill directive (1999/31/EC). Construction material for the final cover construction of these sites is scarce due to the high amounts needed and the demands of the respective landfill class. The estimated need comprises 100 million tonnes only in Sweden (Andreas et al., 2005). Therefore the use of secondary construction materials from different industries is explored. Especially steel industry slags seem to be suitable for applications in geotechnical constructions as for example landfill cover constructions for nonhazardous waste landfills. This is assumed to their high bulk density, low permeability and high strength (Motz and Geiseler, 2001). Investigations of the leaching behaviour by Motz and Geiseler (2001) have shown that only the pH-value had an environmental impact. Significant leaching of elements could not be proved. Steel slags are easily accessible. Different slags are produced during steel production from which electric arc furnace (EAF) slag and ladle slag are investigated in this study. The aim of this literature review is to determine possible mineral phases occurring in steel slags, the formation of these phases and under which conditions transformations can occur. Factors influencing these alterations shall be outlined. Furthermore, analytical methods to measure mineral phases are proposed, explained and discussed if they can be used for these investigations. Among other things cement reaction, and crystal and amorphous structures of the minerals shall be examined. Special focus is put on X-ray diffraction (XRD) and Infrared (IR) Spectroscopy. What and how much information about mineral phases of steel slags can be gained by using these analysis methods? Finally, desirable properties are defined that steel slags should have when used in a landfill cover construction. Possible advantages as well as disadvantages of the analysis methods are discussed and literature data about steel slag analyses are collected. Finally, an attempt of defining desirable properties of the steel slags with regard to their use in a cover construction will be undertaken.

APPENDIX II

2 ORIGINS AND FORMATION OF ELECTRIC ARC FURNACE AND LADLE SLAG


Different slags arise as a by-product during the production of different steels types. The steel industry tries to minimize the generation of slags but they are not completely avoidable.

2.1 Electric Arc Furnace slag (EAF-slag)


EAF slags originate from steel mills where the manufacturing process is based on scrap metal and an electric arc furnace is used. The electric arc furnace contains scrap, iron, alloys and slag formers (Beskow et al; 2004). In Figure 1, the steel production process by the scrap route is shown. The power of three graphite electrodes producing electric arcs is used to melt the material and to form steel. Removal of phosphorous, sulphur and silicon as well as reduction of carbon is initiated by lancing oxygen into the melt [4]. Slag formers are added to the furnace from below and from the sides. The formed slag products, consisting basically of oxides, will rise to the surface due to their lower density. The deoxidisation products are integrated in the slag. These refining processes would take long time, if not an excess of oxygen is provided for the reactions. Later this excess oxygen has to be removed again. The steel is tapped into the ladle (also called converter), which is a vessel used to transport the molten steel to the ladle station. There, further processes are initiated to increase steel quality (secondary metallurgy).

2.2 Ladle slag


After being treated in the EAF furnace, tapped in the ladle and slag being removed from the ladle (tapping of EAF slag), the steel is further treated at the ladle station. In the ladle the chemical composition of the steel is adjusted, the temperature and composition of the melt are homogenised and further removal of phosphor, sulphur and other disturbing trace elements is performed. Steel containing excess oxygen will form gas bubbles during solidification leading to internal holes. To avoid this, the steel is deoxidised with aluminium wire or bars. Aluminium and silicon (in the form of ferro silicon) have a high oxygen affinity and are

APPENDIX II

therefore used for deoxidisation. After that, slag formers (dolomite and lime) and aluminate are added again. Depending on the steel type various alloys are given to the steel. The steel is heated up to about 1925 K and stirred at the degassing station under vacuum conditions (Figure 1) to ensure homogeneity and to remove nitrogen and hydrogen. Stirring is done by induction and through circulation of argon gas. Due to further refining the steel is treated by inductive stirring a second time during which inclusions grow and are removed (Beskow et al., 2004). In the last manufacturing process, called uphill casting, the hot steel is casted in moulds for solidification. The melt in the moulds rises from the bottom to improve the cooling process of the steel.

Figure 1. Flow chart of the steel making process at Uddeholm Tooling Ltd. (a) electric arc furnace (b) ladle furnace (c) vacuum degassing (d) uphill casting (Beskow and Du Sichen; 2004)

3 REUSE OF STEEL SLAGS


As for other secondary materials, the reuse of steel slags helps to conserve natural construction materials and to prevent emissions to the atmosphere. But for the time being, industrial by-products as steel slags are classified as waste in Europe. The definition of waste is constituted in the Council Directive 75/442/EC and amended by the Council Directive 91/156/EC. That definition complicates the marketing and use of slag as a product. Nevertheless, there is a discussion going on about such terms as endof-waste and future definitions in regulations. This discussion is necessary and probably a never-ending process, because due to research new treatment methods are developed. Innovations in material science help to conserve the environment and lead to

APPENDIX II

new application fields of materials. It is intended to change the definition of waste in the way that slags will be considered as by-products and are not classified as waste anymore. Slags from steel industry have found fields of application nowadays. If slags are treated further, e.g. by different cooling methods, stabilization methods or crushing, their properties can be optimized. Different treatments of slags lead to different slag types that are likely to have differences in their properties (Tossavainen, 2005a). Respective treatment techniques are: quenching rapid cooling air cooling slow cooling granulation pelletisation foaming proper solidification with a specified heat treatment separation, crushing, sieving and milling.

Tossavainen (2005a) concludes that the cooling conditions (as well as the chemical composition) determine the formation of a crystalline or amorphous mineral structure, which furthermore influences durability, solubility and reactivity of the slags (see chapter 4.2). Interestingly, steel slags, which have been treated by one or more of the above listed treatment techniques are not included in the European Waste Catalogue (EWC) established by the Commission Decision 2000/532/EC according to a position paper of the European Slag Association called Euroslag (2006). The EWC assigns a number to all types of materials which can be seen as waste. However, a material stated in the EWC is only defined as waste, if the definition of waste stated in the above mentioned Council directives applies.

APPENDIX II

3.1 Generation and utilisation of steel slags in Europe


The chemical and physical properties determined by the production process in the steel mill and will influence the possibilities for utilisation. For instance, the type of slag formers added to the melt (e.g. dolomite or lime) highly influences the chemical composition. This means that different steel production processes result in different slags. On the other hand Motz and Geiseler (2001) state that BOF5 and EAF slags from different sources within Europe [] are generally comparable and independent of their producers. This indicates that nowadays steel manufacturers make big efforts for slag treatment so that desirable properties are achieved. Figure 2 shows that steel slags in Europe comprise mainly BOF slags and EAF slags but also 9 % of secondary steel slags to which ladle slag and argon oxygen decarburisation (AOD) slags belong to. Secondary steel slag 9% EAF slag 29 % BOF slag 62 %

Figure 2. Types of steel slags generated in Europe 2004 (Euroslag, 2006) The amount of generated steel slags in the EU, Germany and Sweden is shown in table 1. According to these data, Germany produced about 40 % of all steel slags in 2004.

Basic Oxygen Furnace

APPENDIX II

Table 1. Steel slag generation in EU, Germany and Sweden Amount Year [million tonnes] EU Germany Sweden 2004 2004 2002 15.2 6.22 0.896

Reference Euroslag (2006) FEhS (2005) Moosberg-Bustnes [5]

The most common reuse of steel slags is as aggregates in road constructions, e.g. ashaltic or unbound layers according to data from Euroslag (2006) shown in Figure 3. Almost one fifth of steel slags are interim, i.e. temporarily stored which is done mainly to observe their properties over time but also because no industrial consumer who wants to reuse the material has been found yet. 11 % of the slags in the EU are finally deposited on landfills. To a small extend slags are also applied in the production of lime fertilizer and hydraulic engineering.
3% 3% 1% 45%

6% 11%

14% 17% road production final deposit hydraulic engineering interim storage others cement production internal recycling fertilizer

Figure 3. Utilisation of steel slags in Europe 2004 (Euroslag, 2006) The amount of reused steel slags varies considerably from country to country, due to differences in chemical composition of the slags and national environmental regulations. Motz and Geiseler (2001) reported that 35 % of the 12 million tonnes of produced steel slags were still dumped in Europe in 2001. In 2004, only 11 % of the 15.2 million tonnes produced steel slags were dumped. If one adds the 17 % interim stored steel slags, about 28 % of the European steel slags do not have found any field of application yet.

APPENDIX II

Conditions as relatively abundant resources of high-quality rock material as in Sweden are playing a major role in reuse of slags. According to Moosberg-Bustnes [5], in Sweden 44 % of steel slags were finally deposited in 2002. In Germany, data are collected by the FEhS-institute being a research association for building materials (former Forschungsgemeinschaft Eisenhttenschlacken e. V.). Utilisation data for 2004 are given in Figure 4 below. According to FEhS (2005), 54 % of steel slags are used as building material in roads, hydraulic engineering, earth-works etc., 17 % are landfilled and further 4 % are interim stored.

54%

8% 4%

17% 5% 12%

internal recycling/circuitry buidling materials interim storage

fertilizer others final deposit

Figure 4. Reuse of steel slags in Germany in 2004 (FEhS, 2005) In Germany the development of utilizing slags for construction purposes begun very early. Already, in 1936 a motor highway in Saxony, has been build with Portland cement mixed with slag (note of the author: probably blast-furnace slag) as an additive. It showed a very good durability under all conditions (Ylipekkala, 2005). If slags shall be used in road construction, they have to fulfil certain mechanical and environmental requirements. The required properties and the corresponding test methods are stipulated in European standards for aggregates and road materials by the European committee of Standardisation (e.g. tests for chemical properties of aggregates - CEN EN 1744). A decisive property for the reuse in road construction is volume stability, which expresses the volume increase during and after the construction process. Several treatment methods to assure sufficient volume stability are shortly described in Motz and Geiseler (2001).

APPENDIX II

Fine milled quenched slag powders are also applicable as additives in cement industry (Ylipekkala, 2005), but mostly BF slags are used for this application. As shown in Fig. 3, only 1 % of steel slags are used as additive in cement.

3.2 Utilisation of steel slags in a landfill cover construction


The landfill cover construction tested in the Hagfors/Uddeholm project at Lule University of Technology is shown in Figure 5 (Andreas et al., 2005).

POSSIBLE MATERIALS

~ 0,3 m Vegetation layer: plant colonization, water magazine,


protection against erosion 1.5 m Protection layer: water magazine, protection against desiccation, freezing, root penetration, erosion of the layers below

SOIL, COMPOST SOIL, DIGESTED SEWAGE SLUDGE MIXED WITH THE FINER FRACTION OF SLAG

Geomembrane (~ 0,5-5 mm): layer separation

~ 0.4 m Drainage layer: collection and discharge of percolation


Geomembrane
water, prevent water standing on liner

COARSE SLAG (EAF), CRUSHED CONSTRUCTION DEBRIS LADLE SLAG MIXED WITH EAF SLAG

1.0 m Barrier layer, liner: minimize gas and water transport


Geomembrane

0.5 m Gas drainage, foundation layer: surface adjustment, load distribution, gas transport

COARSE SLAG (EAF)

Figure 5. Layers and their functions in a cover construction with a mineral liner; examples for possible alternative materials (Andreas et al., 2005) The most critical element of a landfill top cover construction is the liner layer (also called barrier layer). Prevention of water and oxygen infiltration into the waste and uncontrolled leakage of gas out of the landfill are the main tasks a liner has to fulfil. According to the recommendations of the Swedish Environmental Agency (RVF, 2002), the liner has to have a thickness of at least 0.5 m, whereas the whole cover construction should have a thickness of at least 2.5 m. The prevention of water infiltration shall be reached through minimizing percolation of water through the cover system by impeding infiltration through it (direct function) and promoting storage or drainage of water in the overlying layers (indirect function). Runoff, evapotranspiration and internal drainage impede water from reaching the liner.

APPENDIX II

Critical aspects affecting the performance of the liner are quoted from Koerner and Daniel (1997). According to them, cover performance is limited by: cracking due to desiccation, deformations from waste settlement, or seismic motions (e.g., with clay), root penetration, resistance to gas migration, slope stability, creep of all materials (clay, bentonite, geomembrane, asphalt) and service life (geomembranes and asphalt).

The liner material has different functions (Tham et al., 2003). As a high dense cover, the used construction material must have a low hydraulic conductivity and a high dry density. A high density can also be achieved if coarse and fine materials are mixed according to the Fuller curve and compacted. The liner material should not contribute to an increased contamination of the leachate. The atmosphere in a landfill can contain CO2 up to about 50 vol.-%. This leads to a carbonation of the cover material and may decrease its permeability. Todorovic and Ecke (2005) investigated carbonation as an important weathering process for MSWI ash and the effect of it on the release of critical components. They reported that alkaline waste materials are unstable under atmospheric conditions. Hence, weathering will change their mineralogy. According to Tham et al. (2003), the most critical factors for liner performance of secondary construction materials as e.g. incineration residuals are chemical interactions and the resistance to different settlements. If the construction material contains hydraulic minerals, the hardening during curing can cause shrinkage. To reach a low permeability, a liner material should be easily compactable, i.e. an even grain size distribution is necessary (Herrmann et al., 2005). Clays, bentonite mats or sand-bentonite mixtures are materials often used. Geo membranes serve to separate the different layers of the cover construction. Steel slags could be used in the protection layer, the drainage layer, the liner and the gas drainage layer. Of course, each layer has different requirements to the construction material. For fulfilling the functions of the protection layer (e.g. water storage, prevention of desiccation, freezing and erosion) the material needs to have a fine

APPENDIX II

10

structure and contain some organic material. In contrast to the protection layer, both of the drainage layers require a coarse fraction of steel slag. Therefore, EAF slag shall come into use as a part of the protection layer (fine fraction), both of the drainage layers (coarse fraction) and in the liner in mixture with ladle slag (fine fraction). Liner materials as ashes or slags often contain a high amount of carbonates, which are formed after hydration and carbonation of calcium compounds. Afterwards, the dissolution of formed carbonates while reacting with water that have percolated through the overlaying layers can become important in landfills (Marfunin, 1998). The molds of the dissolved carbonates will become additional pore spaces for gases evaporating through the cover. Additionally, CO2 can break up new flow channels leading to an increasing permeability. This is called fracing.

4 MINERAL PHASES
A phase is any portion of a system that is physically homogeneous within itself and is mechanically separable from the other portions. A pure mineral consists of a single phase; a rock is a system of mineral phases, i.e. the phases are the individual minerals. In this study mineral phases of steel slags shall be investigated. Up to now, little literature is available directly focusing on mineral phases of steel slags. Furthermore, an overview shall be given not just about the mineral phases but also about their influence on slag properties. Steel slags are known for having similar chemical compositions as cementitious material (Shi and Qian, 2000; Bvermann, 1997; Fllmann, 1997) and Portland cement, a special cement type (Murphy et al., 1997). Both steel slags and cement contain lime, silica, aluminate and magnesia. That is why steel slags can be regarded as a weak Portland cement clinker (Shi, 2000) and cement phases play a major role in slag chemistry. The different fractions lime, silica, aluminate and magnesia will differ for different steel slags. Shi also concluded that the variation of the mineral composition of steel slags origins from the highly variable chemical composition of steel slags.

APPENDIX II

11

The occurrence of minor elements in steel slags depends on the production process in the steel mill, i.e. which type of steel was produced and from which part of the manufacturing process the slag has been tapped (Caley and McDonald, 2001). It is also possible to calculate the mineral composition by knowing the chemical compounds. An example for cement is given in Czernin (1964). But with this method, just assumptions are possible, as already marginal variances in the chemical composition can cause strong displacements in the mineral composition.

4.1 Mineral phases of cement


Cement is a hydraulic binder. Binders are finely ground mineral substances, that after mixing with water cure to a rock-like, water-resistant material. The term hydraulic points out that the binder not just cures and develops strength by being abandoned to air, but also under water. A very common type of cement, used widely in manufacturing of concrete, is Ordinary Portland cement (OPC). It is produced by heating a mixture of limestone and clay in a rotary kiln at temperatures of 1450 to 1550 C. One reaction in the kiln producing so called quick lime is decarbonation of calcite, also called lime burning. CaCO3 Calcite CaO + CO2 quick lime gas

The compounds formed during the high temperatures are called clinker minerals. After the kiln, the material is cooled, 5 % of gypsum is added and the material is ground to OPC. Under normal temperature conditions only CaSiO3 would form. But the high temperatures induce the attachment of further lime to silica. The clinker and mineral phases, their properties and the associated fraction in OPC are presented in table 2 below. The contents of free lime and free magnesium oxide have to be limited in a construction material, because volume stability is very important under these applications. Expansion after contact with water in steel slags is most likely caused by these two compounds. (Tossavainen, 2005b).

APPENDIX II

12

Table 2. Clinker and mineral phases in OPC according to Knoblauch and Schneider (1992) Clinker phase Cement Mass fraction (%) in Properties (mineral phase) nomenclature cement clinker Tricalcium silicate Dicalcium silicate C3S Fast curing, high heat of hydration, high strength Slow, continuous curing C2S Low heat of hydration, high strength Fast reaction with H2O Tricalcium aluminate High heat of hydration, C3A low strength, susceptible to sulphate waters Tetracalcium aluminate ferrite Free CaO (free lime) Free MgO (periclase) C M C4AF Little and slow curing, resistant to sulphate waters If high amounts present internal expansion If high amounts present internal expansion 0.1 - 3 0.5 - 4.5 4 - 14 7 - 15 0 - 32 45 - 80

During all cement production processes, large amounts of CO2 are released. According to Wenk and Bulakh (2004), 8 % of the worlds industrial production of CO2 is emitted by the cement industry. Hydration While mixing cement with water, the cement converts to a fluid, plastic suspension called cement-paste. Paste refers to a mixture of cement and water in such proportions, that setting and hardening (also called curing) occurs. The chemical reactions occurring between water and cement are referred to as hydration. The water is taken up and integrated in the solid structure. These reactions continue over a long time up to years and with time, the strength of the cement increases. The most important changes in

APPENDIX II

13

mineral composition and microstructure shall be illustrated shortly. One exemplary hydration process, called lime slaking, is shown below. CaO + H2O Ca(OH)2

The hydration of lime and silica leading to calcium silicates is: CaO + SiO2 + H2O CaSiO2(OH)2 Both of these reactions are proceeding during the hydration of cement minerals. The hydration of tricalcium silicate shall serve as an example. 2 Ca3SiO5 + 7 H2O 3 CaO.2SiO2.4H2O + 3 Ca(OH)2 + 173.6kJ Calcium silicate hydrate Calcium hydroxide heat

Tricalcium silicate water

One reaction product is hydrated lime (calcium hydroxide). Hydrated lime takes up 20 % more space than CaCO3. That causes disruption of the whole structure and the material falls apart. Depending on the amount of water, it either turns into a powder or a suspension (lime water). Hydration is an exothermic process. The heat of hydration of lime is 280 cal/g, i.e. one gram of lime can raise the temperature of 280 g of water about 1 C (Czernin, 1964). Some further comments about the hydration process and the heat development are explained in Chapter 5. The most important mineral phases in cement as well as the hydration products are presented in table 3.

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Table 3. Main mineral phases in cement with chemical compounds and corresponding cement nomenclature

Clinker phase (mineral phase)


Tricalcium silicate

Mineral name
Alite

Chemical compound
3CaO*SiO2 2CaO*SiO2 3CaO*Al2O3 4CaO*Al2O3*Fe2O3 CaO*SO3*2H2O CaO*H2O No well defined compound (changing composition)

Cement nomenclature
C3S C2S C3A C4AF

Dicalcium silicate Tricalcium aluminate Tetracalcium aluminoferrite Calcium sulphate dehydrate Calcium hydrate Calcium silicate hydrate Tricalcium aluminate trisulfate hydrate (Trisulfate)

Belite

Celite or Brownmillerite Gypsum

C S H2 CH C-S-H

Portlandite -

3CaO*Al2O3*3CaSO4*32H2O C3A*3C S *H 32 Ettringite or 6CaO*Al2O3*3SO3*32H2O or C6A S 3 H 32

During the first minutes of the hydration reaction, the oversaturated lime-compounds (formed during high temperatures) in OPC mainly tricalcium silicate and dicalcium silicate go into solution. The solution becomes saturated and large crystals of calcium hydroxide (portlandite) and needle-shaped crystals of ettringite are formed. This is illustrated in Figure 6. The possible subdivision of the curing process in dormant period, setting and hardening period can be explained by the mineral changes.

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Figure 6. Changes in cement microstructure during hydration (Wenk and Bulakh, 2004) Because portlandite crystals take up 20-25 % of the volume, strength and durability of the paste decreases. Afterwards, small crystals of calcium silicate hydrates (C-S-H) are formed by the disintegration of calcium silicates. The particles size decreases and colloids are developed which have a much higher specific surface. The C-S-H does not only take up hydration water (in its structure), but also binds water on the surface by adsorption (Krenkler, 1980). Such substances are called gels, because of the high amount of adsorption water compared to the small size of the particle itself. The composition of C-S-H varies with temperature, age of hydration and the water/cement ratio (Wenk and Bulakh, 2004). Factors influencing the rate of cement hardening are identified by Dobrowolski (1998) as the following ones: Chemical and physical properties Curing conditions (e.g. temperature, moisture during curing, time) Water/cement ratio (affecting the ultimate strength)

According to Dobrowolski (1998), a high water/cement ratio produces a paste of high porosity and low strength. After the main hydration reactions, the hardened cement paste not only contains chemical bound hydration water, but also physical bound gelwater and free capillary water (Grbl et al., 2001). The clinker minerals (see table 1) are present in certain modifications. For example, the mineral belite (C2S) can exist as -C2S, -C2S and -C2S, each of them having slightly different crystal dimensions. Which form is present depends on the temperature.

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During cooling of a melt, the -phase present at very high temperatures changes to the

- phase and further to the -phase (Rhling et al., 2000).


The main parameters determining the development of strength according to Grbl et al. (2001) are the chemical-mineralogical composition and the grinding fineness. The chemical-mineralogical composition and the grinding fineness interact with each other. If a material contains less reactive calcium silicates, grinding can provide a larger reactive surface and the reaction rate increases (Rhling et al., 2000). However, Czernin (1964) states that the chemical composition is of minor importance for the final strength. The hydraulic behaviour of materials used in cement industry can be very different. Often, additives are given to the cement in order to influence properties as for example curing behaviour (acceleration or retardation of curing), workability and strength. The hydraulic behaviour depends on the CaO/SiO2 ratio. Rhling et al. (2000) describe a material as puzzolanic if it has a CaO/SiO2 ratio of at most 0.5 (table 4). Table 4. Hydraulic behaviour or different materials (Rhling et al., 2000) CaO/SiO2 ratio Puzzolanic Latenthydraulic Hydraulic 0 - 0.5 0.5 1.5 1.5 2.5 2.5 4.0 Hydraulic behaviour Very low, needs an activator Low, needs an activator Slow curing Fast curing

Puzzolans can be of natural origin, e.g. high silica and/or high alumina soils of volcanic origin. Artificial puzzolans have a hydraulic reactivity developed through thermal processes including fly ash which comes in use in cement production as an additive. Cement additives used are for example fly ash, silica fume, blast furnace slag, oil shale and limestone (Rhling et al., 2000). Often gypsum is added to various cement types.

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A comparison of the chemical compositions of the some of the materials mentioned above can help in further understanding possible similarities in their properties. It is necessary for classifying materials and for distinguishing them in a phase diagram. The chemical compositions of OPS, BF slag and fly ash are shown in table 5. The main oxide is marked by a grey background. Table 5. Chemical composition of certain materials used in cement industry (according to Knoblauch and Schneider, 1992) Fly ash Chemical BF slag from black coal OPC compounds (incl. SO3, Mn2O3) (waterquenched) combustion (mass-%) (incl. SO3, Cl) SiO2 Al2O3 CaO Fe2O3 MgO Alkalis 18 - 24 4-8 61 - 69 1-4 0.5 - 4 32 - 40 10 - 16 40 - 45 up to 5 45 - 55 25 - 30 2 - 6.5 5 - 10 23 3-6

With the help of table 5, OPC can be classified as hydraulic material with a fast curing behaviour, BF slag as latent hydraulic and fly ash as puzzolan of artificial origin. Another type of comparing material compositions are phase diagrams. Figure 7 shows the ternary phase diagram of the CaOSiO2Al2O3 system.

SiO2

Al2O3

CaO
Figure 7. Phase diagram of CaOSiO2Al2O3 system

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Each axis of the phase diagram shows a different binary system, i.e. the three binary systems CaOSiO2, CaOAl2O3 and Al2O3SiO2 are included. The little sketch at the right presents which compound of the binary system of each axis increases. Mineral phases can be associated to a point on the axis. For example, the binary system CaO SiO2 includes the phases 100 % CaO, C3S, C2S, C3S2, CS and 100 % SiO2 (Caley and MacDonald, 2001). In the phase diagram, fly ash is orientated further right compared to slags or Portland cement. The region around that part is presented by the puzzolans, while slags as basic BF slag have a higher CaO/SiO2 ratio and therefore are latent hydraulic. Slags with relatively high silica content are acids. Aluminious cement contains up to 50 % of alumina and therefore mainly consists of calcium aluminates, instead of calcium silicates as the other cement types. This cement type has a very fast hydration process and can bind about twice as much water as other cements (Grbl et al., 2001). Mixtures of aluminous cement with calcium hydroxide (slaked lime) or OPC have only moderate final strength after curing (Karsten, 1997). The main mineral phase of aluminous cement is calcium aluminate which after hydration forms calcium aluminate hydrate. Dicalcium aluminate hydrate is responsible for the fast hydration and fast curing, but it is not a stable hydration product. Under warm and humid conditions (over 22 C), aluminate hydrate and water are separated, dicalcium aluminate hydrate forms, strength and volume decrease and porosity increases. Gases and water can react easily with the cement, therefore pH and final strength decrease. For load-bearing components, it is not allowed to use aluminious cement (Knoblauch and Schneider, 1992). Mhmel et al. (1998) stated that the hydraulic properties of cement to a large part depend on the ratio of calcium aluminate phases. Mixtures of synthesised calcium monoaluminate (CA) and calcium dialuminate (CA2) have been analysed with differential calorimetry analysis (DCA), XRD and nuclear magnetic resonance (AlNMR). The question of this study was how hydration of one aluminate phase influences the second phase if they are mixed in different ratios. Measurements included heat development during hydration over 28 days, strength, specific surface, rate of reaction and hydration products of 100 % CA and CA2 and three mixtures (20/80; 50/50; 80/20). One result was that the specific surface of hydrated CA2 is much larger than for CA. That probably explains the long reaction period of CA2 during hydration in Figure 8. As

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acc. to Mhmel et al. (1998) a high specific surface indicates a good penetratable product layer around the calcium aluminate particles, which allows their further hydration6.

duration of hydration [hrs]

duration of hydration [hrs]

Figure 8. Differential calorimetric analyses of CA, CA2 and corresponding mixtures (Mhmel et al., 1998) Another interesting fact resulting from specific surface analyses was that the hydration behaviour of the pure phases did not correlate with the behaviour of the mixtures. The CA2-rich mixture had only a relatively small specific surface. Hydration products furthermore included amorphous as well as crystalline hydration products from which especially the high amount of amorphous phases influenced the reaction rate. The XRD experiments lead to the conclusion that after hydration of CA CaH10 was formed, whereas hydration of CA2 rather induced formation of Al(OH)3. The CA reaction rate increased in the mixtures compared with the pure CA. The opposite applied to CA2. In the next chapter, the chemical composition and mineral phases of steel slags are investigated.

German quotation: Eine hohe spezifische Oberflche ist nmlich ein Zeichen fr eine gut penetrierbare Produktschicht um die Calciumaluminatkrner, die deren weitere Hydratation erlaubt.

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4.2 Mineral phases of steel slags


As stated in the terminology chapter, the term steel slags includes EAF slags, ladle slag and AOD slags. But because only EAF and ladle slag are included in this study, the chapter is restricted to the mineral phases of EAF and ladle slag. Studies focusing on mineral phases of EAF slags were performed by Murphy et al. (1997), Motz and Geiseler (2001), Shen H. et al. (2004) and Tossavainen (2005a). These studies also reported about BF slags (Murphy et al., Tossavainen), BOF slags (Motz and Geiseler) and natural rock materials (Motz and Geiseler, Tossavainen). Motz and Geiseler (2001) classified EAF slags as calciumsilicatic with an CaO content in the range of 25-40 % and a SiO2 content of 12-17 %. Additionally, free MgO and free lime (CaO) is present. They outline MgO and free CaO as a key criterion for the application of steel slags in civil engineering. The main mineral phases of EAF slags as well as for BOF slags are dicalcium silicate (C2S), dicalcium ferrite (C2F) and wustite (FeO) (Motz and Geiseler, 2001). The chemical composition of two different EAF slags is given in table 6. Table 6. Chemical composition of two EAF slags (Motz and Geiseler, 2001) EAF slag with low MgO EAF slag with high MgO [%] CaO SiO2 Al2O3 MgO MnO P2O5 Fetotal CaOfree 30 - 40 12 - 17 4-7 4-8 <6 <1.5 18 - 28 <3 [%] 25 - 35 10 - 15 4-7 8 - 15 <6 <1.5 20 - 29 <3

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The manufacturing of different steel types leads to different slag types. The chemistry of steel slags depends not just on the amount of alloys given to the steel, but also which slag forming agent is used. A compilation of the chemical composition of different EAF slags found in literature is shown in Figure 9.
35 30 25 20 15 10 5 0 Ca Si Al Mg Mn Fe
Uddeholm (EAF) Caley/Mac Donald (EAF) BMU (EAF h-a) Fllman/Hartln (EAF) Shen (EAF) Motz (EAF-low MgO) Murphy (EAF) BMU (EAF l-a) Motz (EAF-high MgO)

wt - %

l-a slag from low alloyed steel h-a slag from high alloyed steel

Figure 9. Compilation of literature data about main elements in EAF slags (BMU data [6]) The differences between OPC and steel slags are explained by Murphy et al. (1997). The author states that steel slags contain more iron oxide than OPC. The valence state of iron oxide determines the morphology and cementitious properties. The iron is present in the form of divalent and trivalent iron. Furthermore, steel slags consist of higher amounts of free lime. Free MgO and CaO are hydraulic phases and will lead to expansion of the structure after contact with water (fluid or gaseous). Expansion of free CaO is occurring earlier than that of free MgO (Murphy et al., 1997). The MgO content of EAF slags can be higher compared to BOF-slags due to the reaction with the refractory lining but also depends on the eventual use of dolomite as slag forming agent. Murphy et al. (1997) investigation results of EAF mineral phases are presented in table 7.

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Table 7. Predominant mineral phases associated with steel slag (Murphy et al., 1997) Melting Formula 3CaO*SiO2 2CaO* SiO2 Name Alite Belite Belite (Larnite*) Bredigite Dicalcium ferrite Brown millerite Wustite Periclase Lime Iron oxide Magnesia Calcia 2800 2570 Calcium ferrite 1430 1410 Synonym Tricalcium silicate Dicalcium silicate point (C) 1900 2130

-2CaO*SiO2
-2CaO*SiO2
2CaO*Fe2O3 4CaO*Al2O*Fe2O3 FeO MgO CaO

* -Ca2OSiO4 = Larnite (Tossavainen, 2005a) Additionally, the melting points of some phases are given to indicate which mineral phases solidify first when the melt in the converter is cooled down. Solidification of periclase happens first while brown millerite solidifies at last. Murphy et al. (1997) conclude that the limited cementitious properties of steel slags result from a lack of tricalcium silicate and a surplus of wustite, which has the ability of taking up calcium. Therefore, calcium is not available for the formation of tricalcium silicate anymore. Wustite solid solutions (see Terminology) are the main mineral phases in steel slags according to Murphy et al. These phases do not occur in Portland cements and do not form hydraulic minerals. Therefore, they have no cementitious properties. The matter is different with the ferritic minerals, e.g. calcium ferrite, calcium aluminate ferrite. They are formed by the mineral phase hematite (Fe2O3) and are hydraulic. In their studies, Shi and Qian (2000) summarised the relationship of basicity, reactivity and mineral phases of steel slags. According to their findings, the reactivity of steel slags as well as the content of free CaO increases with basicity, i.e. the CaO/SiO2 ratio. Slags with a low reactivity contained olivine (0.9 < CaO/SiO2 < 1.5) and merwinite (1.5 < CaO/SiO2 < 2.7). Medium reactive slags (CaO/SiO2 < 2.7) consisted of dicalcium silicate while high reactive slags with a CaO/SiO2 ratio > 2.7 were build of tricalcium

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silicate. With orientation towards metal recovery, Shen H. et al. (2004) analyzed the mineral phases of EAF slag. The author found bredigite (Ca7Mg(SiO4)4), merwinite (Ca3Mg(SiO4)2), akermanite (Ca2MgSi2O7) and gehlenite (Ca2Al(AlSi)O7) being the main minerals. Also magnetite and chromite (Fe, Cr and Ni phases) were recorded after magnetic separation of the original sample. These results were also recorded by analyses of Tossavainen (2005b), who besides other minerals (included in table 4) identified Merwinite and Larnite ( -Ca2OSiO4) as the main phases of the EAF slag samples. All slags contained hydraulic minerals and glass, which together with aqueous solutions tend to form stable hydrated phases. Tossavainen (2005b) also found an increasing number of mineral phases as cooling time and therewith other influencing factors increase. As a result of this, a more homogenous slag with few phases is formed after rapid cooling e.g., by water granulation. Krenkler (1980) also reports that a rapid cooling leads to a glassy structure (of BF slag) while slow cooling supports crystal growth. This example shows that appropriate treatment techniques make it possible to control the properties of slag materials.
wt - % 35 30 25 20 15 10 5 0 Ca Si

Uddeholm - ladle slag

BMU - ladle slag

Al

Mg

Mn

Fe

Figure 10. Composition of Uddeholm ladle slag and BMU data about ladle slag [6] Mineralogical compositions of ladle slag have been investigated by Caley and MacDonald (2001). One ladle slag with additional fluorspar (CaF2) and one ladle slag with nepheline syenite (igneous rock containing the mineral nephelite, which has the formula (Na, K)AlSiO2) were looked at. SEM analyses showed the presence of cement phases as tri- and dicalcium silicate in the fluorspar slag and the minerals merwinite and monticellite in the nepheline syenite slag.

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4. 3 Alteration of mineral phases


Alteration of minerals in nature occurs mainly due to weathering processes. A primary mineral undergoes transformation and a secondary mineral is formed. This is also called mineral aging. Factors as temperature, pressure, the chemical, physical and biological environment and also humidity influence these alterations. The application of steel slags in a liner construction will lead to alterations of the primary mineral phases over time. An assessment of resulting secondary mineral phases shall be made in this chapter. For this, a simplification of the expected surrounding conditions is necessary. The reaction rate of mineral transformations can differ according to the present conditions. This is especially the case in a liner, as there are no evenly distributed conditions, for example a changing water content in the pores over time and place. Again, mineral transformations of well ascertained similar materials can be adjuvant to assess secondary phases of steel slags. In the liner, the main gases influencing the alteration processes of minerals are considered to be CO2 and CH4. Carbonation and methane oxidation are the respective processes expected to occur in the cover construction of a landfill. Also, the humidity, i.e. the water vapour is of interest for the forming of secondary minerals. The pore solution (including percolates) will react with the (initially present) primary minerals of the liner material. The pore solution gets oversaturated with respect to a certain compound and the primary minerals will become unstable, because of changes in pH, buffering capacity, salinity and redox potential. A certain compound can precipitate and a new secondary mineral will be formed (Marfunin, 1998). From the estimation of the water balance it is expected that 5 % of the precipitation infiltrate through the liner and reach the foundation layer. A quantification of expected methane values cannot be given for the liner itself. About mineral phases of slags, Tossavainen (2005c) states that these minerals probably react with moisture, CO2, etc. during storage und to some degree undergo phase transformations. The author further emphasises the effect of weathering processes and crystal structure on leaching behaviour. Leaching reactions of amorphous slags will differ from the reaction of crystalline slags.

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The reaction of calcium silicate phases with carbon dioxide and moisture is known from cement chemistry. In presence of moisture, carbon dioxide in the air forms carbonic acid (H2CO3). H2O + CO2 H2CO3 The hardening of lime according to the formula Ca(OH)2 + CO2 CaCO3 + H2O or more precisely presented by Ca(OH)2 + H2CO3 CaCO3 + 2H2O (exothermal reaction) is also called carbonation. The carbon dioxide originates mainly from the air (air content about 0.03 %). But the carbonation process does not take place in absence of water (vapour or liquid). The base calcium hydroxide only reacts with carbon dioxide in the form of carbonic acid. Due to the very low carbon dioxide content in the air, carbonation of the whole bulk of a material takes long time. Karsten (1997) states, that for cement, carbonation (hardening of lime) occurring on the surface is finished after about one year. The process is accelerated by a high CO2 concentration in the surrounding air and humidity. However, too high moisture content retards the reaction. Carbonation is proceeding optimally under the influence of heat, good circulation of air, high pressure and high reaction surface (Karsten, 1997). Studies focused on mineral transformations of MSWI ashes were performed by Zevenbergen et al. (1998), Knorr et al. (1999), Hirschmann (1999) and a. o. summarized by Piantone et al. (2004). During weathering of MSWI ashes, reservoir minerals are formed that comprise phases of ettringite, calcium monosulphate, calcium silicate hydrate (C-S-H), brucite (Mg(OH)2) and calcite (see Figure 11).

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Figure 11. Mineralogical evolution taking place during weathering of MSWI bottom ash (Piantone et al., 2004) After two years of weathering, the primary minerals of MSWI bottom ash were transformed into zeolites, after 12 years into clays. However, chemical composition and hydraulic behaviour of the minerals present in MSWI ash vary considerably from steel slags. Less calcium, higher silicon and higher metal fractions are the main differences (Hirschmann, 1999). The hydraulic reaction of MSWI ash is very low and carbonation plays a minor role in the first 20 years. Heavy metals as zinc and lead can be bound to carbonates and get immobilized (Huber et al., 1996). But regardless the differences of the steel slags and MSWI ashes, fig. 10 shows that hydration and hydrolysis reactions as well as mineral alterations occur. Hydrolysis refers to the chemical reaction of minerals with H+ and OH- ions of dissociated water molecules. Mainly carbonates and silicates are broken down by hydrolysis. Particularly, the stability regions of primary and secondary minerals depending on pH are given in Figure 11 above. As mentioned before, dissolved carbon dioxide and L/S ratio (liquid/solid) influence these alterations. Cement phases for example the presented stability region is from pH 9 to 13 are shown as secondary phases. The origin of C-S-H (calcium silicate hydrates) is lime, which in fig. 10 is referred to as primary phase. Nevertheless, in this study, calcium silicate hydrates are referred to as primary minerals in steel slags, i.e. primary phases after hydration. Some theses about mineral alterations of steel slags shall be inferred. Steel slags are mainly consisting of calcium silicates. As it is a basic construction material, the buffer

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capacity (acid neutralisation capacity) of carbonates is expected to play a major role in the beginning of the leaching process. Some important buffering reactions of carbonates, silicates and aluminium hydroxides according to Scheffer and Schachtschabel (1998) are: Carbonates Bicarbonates Primary silicates CaCO3 + H+ HCO3- + H+ (SiO)M + H+ HCO3- + Ca2+ CO2 + H2O (SiOH) + M+ pH 8 6.5 pH 7 4.5 pH < 7

[M+ = 0.5Ca, 0.5 Mg, K, Na] Al-hydroxides Al(OH)3 + 3H+ Al3+ + 3H2O pH 4.8 3

Because of their high specific surface of 10-50 m/g, C-S-H phases also have a high sorption capacity. As mentioned in Hirschmann (1999), the sorption capacity depends on the Ca/Si ratio. Sorption capacity increases with silica content. Concerning this matter, Piantone et al. (2004) writes that carbonate and Fe oxide phases [] can take up metals very efficiently. Hirschmann furthermore attributes a substantial metal uptake to C-S-H and C-A-H phases (Knorr et al., 1999). The buffer is generated by carbonation and metal complexes are incorporated in the lattice of the minerals. If the carbonate buffer is used up and pH decreases, a higher solubility of calcium and a higher heavy metal content can occur in the leachate. The possibility of a release of certain metals already before the buffer capacity is used up, has been investigated by Kersten (1996). The solubility and release of heavy metals is controlled by processes as complexation, ion exchange, precipitation, formation of solid solutions and adsorption (Kersten, 1996). The destruction of carbonates by dissolution of calcium (also called decalcification) through weathering can be assessed by chemical models. Therefore, assumptions are made for parameters as thickness of the slag layer (consisting of carbonates), precipitation in a certain area, infiltration rate in the ground, carbonation rate and calcium content of the slag layer. The solubility rate of calcium is in the range of 16-60 g/m of leachate (Hirschmann, 1999).

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Different authors (a. o. Lahl, 1992; Ecke, 2003b) reported about a period of several thousand years until the carbonate buffer of an assumed slag layer is used up. In how far, aging processes lead to expansion of phases through hydration of free MgO or CaO or clay formation is still unknown. It is probable that chemical compounds preserved in the matrix of the material will get in contact with air and water etc. after some of the matrix already has been diluted. Than, also this CaO or MgO can undergo hydration reactions. According to the theses of Huber et al. (1996), the following processes occur during the alteration of MSWI ash: hydration carbonation microbiological and anorganic oxidation weathering and crystallization.

The focus in the study of Huber et al. was laid at the alterations of MSWI ash. But about alterations of carbonates, i.e. carbonatic material, the author made preditions as well. It was stated that during aging, hydroxids are transformed into carbonates (1st step), e.g. calcium hydroxide into calcite. Afterwards, while the carbonate buffer is reduced, carbonates are transformed into bicarbonates (2nd step). CaCO3 + CO2 + H2O Ca(HCO3)2 Knorr et al. (1999) assumes that only a minor part of the minerals (about 10 to 20 m.-%) will be carbonated at all. However, Huber et al. (1996) resulted that due to artificial carbonation 80 % of the analysed MSWI ashes have been carbonated. The rest did not transform into carbonates, because, a rest of carbonates were integrated in slag particles or glassy compounds. Even if the carbon dioxide content has been increased in the laboratory, the rest of the material did not form into carbonates. Instead, the already present carbonates were transformed into bicarbonates. But the author furthermore assumes that in a landfill over a long time period also these 20 % could get carbonated. As the steel slags from Uddeholm AB investigated in this study are already hydrated after the liner is build, the formation of carbonates of at least a part of the material is expected. As stated before, it takes probably several thousands of years until the carbonate buffer is used up bicarbonates are formed. Huber et al. also suggests pH value as the crucial parameter for estimation of long-term processes.

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5 CALORIMETRY
It is known from past investigations (Shi, 2002), that the slags have curing properties, i.e. which while mixing with water heat due to hydration is released (exothermic reaction). The slag hardens during a certain time depending on the respective composition. The knowledge of heat development after mixing EAF-slag and ladle slag is unknown. This plays an important role not only for the construction time of the liner, but also is assumed to influence the mineral formation (e.g. melting points, solution, and crystallisation). Calorimetry means measuring heat. Here the term heat refers to all kinds of energies that can be exchanged between two systems. A calorimeter is a device for measuring heat, i.e. energy changes. The heat released during a chemical reaction in a liquid media can be measured in a calorimeter. It can be used as an indicator for the heat of hydration released from the system to the environment. A calorimeter measures the energy exchange between the reaction system and its environment. The reaction system is the ongoing chemical process and the environment is presented by the calorimeter and its contents itself. To be able to fulfil the assumption of negligible heat flow between the calorimeter and the surrounding, the calorimeter has to be very well isolated. Under this condition, the energy change during the reaction is equivalent to the heat uptake (respectivily heat loss). The basic equation of calorimetry is

dQ = C * dT
or

Q = C * T = c * m * T
Q......Heat, i.e. energy change [KJ] C......Heat capacity T ...Temperature change c.......specific heat capacity m .....mass [KJ*K 1 ] or [KJ*C 1 ] [K] or [C] [KJ*kg 1 *K 1 ] or [KJ* kg 1 *C 1 ] [kg]

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To calculate the energy change in a calorimeter, the heat capacity of the calorimeter itself is required. It has to be experimentally determined by a standardization procedure where chemicals with a known release or absorption of energy are reacting. With the energy change known, one can further calculate the change in enthalpy H.

H = -Q / m
An example of heat evolution during cement curing is shown in Figure 12. It can be seen that the reaction of pure Portland cement occurs in five stages with the highest heat released in the first stage.

Figure12. The rate of heat evolution of cement hydration at 25 C (Mostafa and Brown, 2005) (1) the initial reaction (2) the induction period (3) the acceleratory period (4) the deceleratory period (5) the period of slow continued

The mechanism of hydration is further explained in Glasser (1996) who states that it is similar for all glassy materials as slag, fly ash and glass [2]. These materials contain Si-O-Si bonds (silanol bonds) which are hydrolysed by OH- ions. Through this first step of alkaline hydrolysis, the network of the glassy material breaks apart. The material reacts with activators as e.g. Ca(OH)2 in cement. Precipitation of the reaction products occurs and the gel-like matrix solidifies. Motz and Geiseler (2001) summarize the hydration of slag as reaction between water vapour and free CaO and/or free MgO forming hydroxides. Depending on the amount of CaO and MgO a volume increase, disintegration of slag pieces and a loss of strength are possible consequences. Tossavainen (2005a) also mentions expansion as a

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consequence of hydration of CaO and MgO. The hydration of MgO takes thereby more time than that of free lime. The heat of hydration for the main clinker phases are given in Knoblauch and Schneider (1992). For the mineral phase C2S, heat of hydration after full hydration is 250 J/g, while it is 525 J/g for C3S. Also, Portland cement releases 375-525 J/g, while aluminous cement releases 545-585 J/g. Tossavainen (2005b) reported about calorimetric measurements of cement mixed with 20 % ladle slag. Untreated ladle slag has been found to retard the heat development curve severely. If the slag was granulated, hydraulic reactivity was higher. The author also concluded that the reactivity of a slag is increased with an increase in the glassy content. Furthermore, water granulation has increased volume-stability. More hydration characteristics analysed with differential thermal analysis of systems of Portland cement and mineral additives (e.g. BF slag) have been reported by Sharma and Pandey (1999). Adjustment of the curing process is important as construction must be finished before curing stops. Mixing EAF and ladle slag is one possibility to do this, as curing time depends on the composition. In cement industry, this problem is solved by adding calcium sulphate and therewith retarding curing. Cement additives generally have to be adjusted to the chemical-mineralogical composition (Grbl et al., 2001).

6 X-RAY DIFFRACTION
X-ray diffraction is also referred to as crystal structure analysis, because the prerequisite, for being able to use this analysis method, is a crystalline sample. The best results are obtained with single crystals, but also crystal powder can be used. The information obtained from the spectrum is the measurements of the unit cell (i.e. the smallest repeating array of atoms in a crystal) and the detailed position of all atoms in the crystal. Therewith the crystal- and molecule symmetry can be derived (Mortimer, 2003).

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6.1 Physical background and sample preparation


To avoid absorption, the XRD method (combined with the powder method) uses monochromatic X-ray beams, i.e. light with a single wavelength. The X-ray beams fall on the crystal planes under a certain angle and are reflected i.e. diffracted according to the Bragg-equation.

n*=2*d*
with n d order of diffraction [1,2,3,...] wavelength distance between the crystal layers angle of incidence / angle of diffraction

(Mortimer, 2003) To diffract X-rays, a lattice plane of the crystal has to be in a reflection position. The short wavelengths of X-rays make them ideal for crystal analysis because their wavelengths (0.1-5 ) correspond to the distance between the lattice planes in crystalline minerals which is roughly 0.3 nm or 3 (Jones, 1987). The distance between two lattice planes is called interplanar spacing or d-spacing. For diffraction, the scattered X-rays must not interfere destructively with each other, what is the case at one particular angle , called Bragg angle, of the incident beam. At this angle, determined by the distance between similar atomic planes, the path-length difference of the X-rays scattered at different atomic planes are integers (n frequently 1) or in other words the path lengths of the scattered rays differ from each other by exact multiples of the incident monochromatic X-ray wavelength (Jones, 1987). As a result, the scattered rays are in phase and interfere constructively. Constructive interference means, that when two waves are in phase, there is a perfect overlap of crests with crests and troughs with troughs. This leads to an intense light beam. The resulting X-ray intensity, measured as 2, is represented by a peak in the diffractogram. The angle represents the angle where constructive interference has occurred.

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Sample powders can be used instead of single crystals as well. The first step of sample preparation is to ground the pure specimen into particles of less than about 50 m in size (Jones, 1987). Diffraction occurs because lattice planes are randomly distributed in the powder, so that at least some crystals of each plane fulfil the Bragg-equation. The X-ray beam falls onto the plane with the Bragg-angle and is diffracted. With the help of a magnet, metallic particles which can cause disturbances while analysing are taken away. The sample is carefully filled in the sample cup. The surface of the sample has to be as even as possible. The sample cup is put in the XRD device. The elements in the mineral are identified with the help of the characteristic wavelength of the diffracted X-ray. The intensity of the radiation states the concentration of the element if quantitative analysis is performed (Jones, 1987).

6.2 Interpretation of one X-ray diffractogram of steel slag


Diffraction patterns of steel slags as shown in Figure 12 are very complex and a variety of mineral phases can exist in the sample. Steel slags can contain crystalline and amorphous phases. Amorphous structures cannot be identified, but the amount of the amorphous fraction can be estimated from a hump of the background of the diffraction pattern at about 2 (2-Theta) from 20 to 40. If a sample measured with XRD contains several minerals, peaks of one mineral will overlap with the peaks of the other minerals. Many crystalline phases are detected and the specimen gives all the diffraction beams simultaneously. This makes the identification procedure of each mineral taking part in the diffraction pattern more complicated. Every crystal phase has its characteristic diffraction pattern. Diffraction patterns of single minerals are recorded in tables and databases. But in a sample, together with other minerals, this diffractogram is modified the more, the more other minerals are present (Jones, 1987). In Figure 13 almost every peak in this diffractogramm of steel slag is caused by more than one mineral (the main peak for example by bredigite and merwinite).

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Figure 13. X-ray diffraction of EAF sample (Shen et al., 2004) The two variables obtained from the computer analysis of the diffraction pattern are the peak position with which the interplanar spacing (d-value) can be calculated and the intensity of the peak. Further examples of XRD patterns originating from steel slag, fly ash and ordinary Portland cement (OPC) can be found for instance in Murphy (1997), Sharma and Pandey (1999) and Shen H. et al. (2004).

7 IR SPECTROSCOPY
The infrared radiation is a part of the electromagnetic radiation. Its range is between the visible part and the microwaves. The most important infrared region in analytical spectroscopy is the mid-infrared region, because there the fundamental vibrations of molecules are observed (table 8). Rotations are possible modes as well. Nevertheless, in fluids and solids rotations are suppressed and only a few compounds exhibit rotational bands.

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Table 8. Regions of Infrared radiation Wave number [cmWavelength [m] Range 1 ] Near Infrared Mid Infrared Far Infrared 13300 ... 4000 4000 ... 400 400 ... 10 0.75 ... 2.5 2.5 ... 25 25 ... 1000

7.1 Physical background of Vibrational Spectroscopy


Some basic principles shall be explained first. If light interacts with matter, three processes are occurring simultaneously, that are reflection, transmission and absorbtion. The intensity of a light beam I0 includes information of all three processes. I0 = Ir + It+ Ia The transmittance of a sample is the ratio of the intensity of monochromatic radiation entering a sample related to the intensity transmitted by the sample: T = I/Io The absorbance A and the transmittance are logarithmically related. Absorbance changes linearly with changes in concentration of an absorbing sample. A = log (1/T) = log (Io/I) = e * c * L Io = Intensity of incident radiation I = Intensity of transmitted radiation e = molar extinction coefficient (= absorbtivity a) c = concentration (mole/l) L = sample pathlength (cm) (= thickness of the sample b)

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The absorbance of a sample written as A=a*b*c is called Bouguer-Lambert-Beer law or commonly Beers law. This is the fundamental equation for spectrometric quantative analysis. Infrared light is absorbed by a molecule or a functional group if a change in the dipole moment occurs as a result of optical excited vibrations in the molecule. To absorb radiation is equivalent with reaching a higher energy state and the associated energy is converted into these types of motions of the chemical bonds (Sherman Hsu, 1997). The dipole moment describes the unequal distribution of the electric charges of a molecule considering their distance. The larger the change in the dipole moment, the stronger is the absorption. The relation between the intensity of the infrared absorption and the dipole moment is given by: IIR ~ q
2

The absorption intensity is proportional to the square of the change in the dipole moment , with respect to the change in the normal coordinate q, which describes the molecular vibrations induced. Molecular vibrations can be imagined by a model. One can consider a complex molecule as a system of coupled inharmonic oscillators (Gnzler and Williams, 2001). The internal degrees of freedom correspond to the number of independent normal modes of vibrations. If there are N atomic nuclei in the molecule, a nonlinear molecule will have 3N-6 and a linear molecule 3N-5 internal degrees of freedom, i.e. modes of vibration. Water for example has a static dipole moment, where positive and negative electric charges are not equally distributed in the molecule. When an electromagnetic field affects the dipole, it orientates itself towards the direction of the field, i.e. the charges experience a static force leading to rotation of the molecule and vibrations in the boundary length. The molecule takes up rotational and vibrational energy from the electromagnetic field. Excitation only takes place, if the vector of the electromagnetic field is not perpendicular to the vector of the dipole moment. The frequency of the

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exciting IR radiation has to correspond to the frequency of a certain molecular vibration. Than radiation is absorped by the molecule (Sherman Hsu, 1997). Unlike water, carbon dioxide has no static dipole moment. The charges are linearly situated (linear molecule), so that the polarizations cancel each other. Nevertheless the carbon dioxide molecule can be excited to vibrations with infrared radiation, so that a dynamic change in the dipole moment occurs. This change in the dipole moment is induced, e.g. during antisymmetric vibrations (Fig. 14). Vibrations, as for example symmetric ones in the CO2 molecule, leading to no change in dipole moment, are infrared inactive. This means they do not absorb infrared radiation.

(a)

(b)

(c)

Figure 14. Vibration modes of the CO2 molecule (a) symmetrical stretching (b) asymmetrical stretching (c) bending As can be seen in Figure 13, a stretching vibration means that the distance between two atoms increases or decreases, whereas an atom bends if it leaves its position on the original bond axis. The CO2 molecule has four normal modes of vibration (three of them IR active) from which one mode is not shown in the figure above.

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The unit widely used for IR radiation is the wave number. It is proportional to the frequency and therewith also to the energy of the electromagnetic field.

~ =

~ ...........wave number [cm-1]

...........wavelength [cm]

............frequency [s-1]
C.............speed of light [km* s-1]

The majority of the investigations with IR spectroscopy focus on organic compounds. The spectra of inorganic substances show few, wide and intense absorption bands (Gnzler and Gremlich, 2002) and in contradiction to organic molecules they are further characterized by absence of C-H stretching and bending bands (Smith, 1999). Smith states that infrared bands of metal atoms [] often appear below 400 cm-1 and that it is usually impossible to tell from a mid-infrared spectrum what metal atoms are present in a sample if the spectrometer does not reach this wave number range. As examples, the author names metal-oxygen stretching and bending vibrations. Also Gnzler and Williams (2001) name this problem by stating that the fundamentals occur in the mid-infrared range, which is the most important infrared region, but simultaneously the fundamentals of heavy, single-bonded atoms and the absorptions of inorganic coordination compounds are found in the far-infrared region. More information of the infrared spectra of carbonates can be found in Gadsden (1975). As summarized by Smith (1999) inorganic spectra consist of high intensity, low wave number vibrations characterized by the lack of C-H stretches and the occasional presence of water bands. However, many inorganic compounds can be identified with IR as well. Often, samples consist of a positively charged metal ion and a negatively charged ion. Due to the high partial positive and negative charges in this ionic bond, the dipole moment is large, and strong infrared bands are obtained (Smith, 1999).

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7.2 Technique of the FTIR Spectrometer


The Fourier Transform Infrared (FTIR) method is a spectroscopic method used to get structural information on materials. The spectrometer contains a device called interferometer. The so called Michelson interferometer is most often used (Figure 15).

Figure 15. Schematical draw of the Michelson interferometer

The interferometer is an optical instrument to split one beam coming from a source into two beams, to shift them sterically by mirrors against each other and to interfere, i.e. recombine them at a beam splitter. From there just one beam is directed towards the sample. After having interacted with the sample, the beam is detected. The detector measures the intensity of the radiation depending on the optical path difference of the two beams. The result is the interferogramm. To calculate a spectrum, the FTIR spectrometer transforms the interferogramm by using the cosine Fourier-transformation. The interferogram is a function of time domain, whereas the spectrum is a function of frequency domains as shown in Figure 16. With the Fourier transformation, time and frequency data can be interconverted.

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Figure 16. Comparison of interferogram and spectrum

For a detailed understanding, literature about FTIR data processing, e.g. Gronholz and Herres (1984) is recommended.

7.3 The DRIFTS method


To measure infrared spectra of powders and other solid materials, Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) is used. Diffuse reflectance means that the incoming radiation is reflected in all directions. The DRIFTS accessory consists of flat mirrors, an ellipsoidal mirror and a sample slide mount where the sample cup is placed in (Figure 17). The IR beam is directed from the flat mirrors onto the ellipsoidal focusing mirror and from there onto the sample. The sample consisting of the slag/KBr mixture reflects the radiation diffusively. The scattered light is collected by the mirrors again and redirected to the IR detector. A high quality DRIFTS spectrum is the results of 10 to 100 sample scans.

Figure 17. Sample accessory of the DRIFTS method

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The material to be examined, consisting of a part of the cured steel slag specimen, is grinded to a very fine powder from which approximately 3 mg of sample are taken and dispersed homogeneously in an appr. 200 mg KBr matrix. Grinding is done by hand with pestle and mortar. The preffered particle size would be the one below the wavelength of the used radiation, to avoid a loss of energy due to scattered radiation. Scattering is recognized in a sloping of the baseline (Smith, 1996). The reason for using potassium bromide is given by the cut-off-frequency of around 300 cm-1 stating there is no absorption of MIR radiation with pure ionic bonds (infrared transparent).

7.4 Interpretation of IR spectra


The first step evaluating a spectrum is to look for measurement parameters as resolution, possible irregularities as spectral manipulations (e.g. baseline correction) and features showing mistakes in the analysis procedure. This can be for instance too much or too less sample, a poorly pulverized sample (for solid samples), unequal distribution of the sample in the KBr or water absorption bands. If a sample consists of a mixture of different molecules, the spectrum gets more complex, similar to a XRD diffractogram. A possible method to simplify the spectrum is purification of the sample. Another method, called spectral subtraction, is used if for instance water absorption bands shall be removed of a spectrum. Another tool for simplifying interpretation is the mathematical comparison of the measured spectrum with a collection of known spectra from a library or a database. The fitting of two similar spectra can be expressed by the hit quality index (HQI). Furthermore, methods of manipulating spectra can be used. Therewith, hidden features can appear, by for instance increasing the resolution of the spectra. A combination of these methods is also applicable (Smith, 1999). However, due to the variety of molecular design and therewith recordable spectra, the molecular structure often can only be explained partially.

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A 10-step approach for interpretation of spectra is given in Smith (1999), from which some advices have already been mentioned above. Further, detailed interpretation help is given in Gnzler and Gremlich (2002). In Figure 18, the terms needed for interpretation are shown within an example. Terms as absorption maximum and shoulder are also used in data tables, where no spectra are given.

Figure 18. Model spectrum for explaining fundamental terms (Gnzler and Gremlich, 2002) 1) Baseline 2) Area between baseline and transmittance 1: background absorption or reflection losses on e.g. on cell windows 3) Absorption maximum, i.e. transmittance minimum and absorption maximum, respectively, of the vibrational bands: all of these synonymous terms serve for labelling the position of maximum uptake of radiation energy in the spectrum by the molecule. 4) Shoulder: two non-separated bands. 5) Disturbances by absorption of CO2 and H2O of the air.

An IR spectrum can be plotted in two ways, first transmittance vs. wave number and second absorbance vs. wave number, as shown on the axes of Figure 17. For the DRIFTS method another transformation from transmittance into Kubelka-Munk units needs to be done, because the law of Lambert-Beer is not valid for diffusive reflection.

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The Kubelka-Munk function is: f (R) = R......capability of diffusive reflection k ......absorption coefficient s.......scattering coefficient Therefore, the y-axis of spectra recorded with the DRIFTS method is in Kubelka-Munk units, which are linear to concentration. If one performs a quantitative analysis of an IR spectra measured using the DRIFTS method, one can relate the radiation intensity to the sample concentration via the Kubelka-Munk function. (1 R) k = 2R s

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8 DISCUSSION
As steel slags and BF slags have cementitious properties, they have been used as filler material for cement (Shi and Qian, 2000; Bvermann, 1997; Fllmann, 1997). That changes the properties of the cement and is the reason why a lot of research of slags is orientated towards this application. A similarity of cement and slags is the presence of hydraulic minerals and the hydration process induced by adding water (Glasser, 1996). However, the hydration reaction is very low compared to cement. Steel slags can contain many different minor elements depending on the steel, i.e. alloys from were it is tapped (Caley and MacDonald, 2001). Therefore, they have to be analysed before applying them as a construction material. Literature about the long-term behaviour of steel slags has not been available in the form of measurements. Therefore, factors for assessing the alteration and ageing processes of the material have been outlined. The focus of this work is put on the mineral phases. They are a. o. influenced by the chemical composition and the slag treatment after the steel tapping. Slow cooling leads to a more crystalline slag, whereas rapid cooling results in more amorphous phases. The slags of Uddeholm have been aircooled and should therefore contain minerals in a crystalline form. But no analyses of the mineral structure have to been performed up to now. Analyses of other slags a.o. by Shen H. et al. (2004) have found minerals in a crystalline form as merwinite, akermanite, gehlenite and bredigite. Granulation of slags can increase the reactivity according to Tossavainen (2005b). But again, this result has been taken from a study where ladle slag was mixed with cement (1:5) leading to nucleation and growth rates, which are almost the same as for pure cement. If this is transferable to mixtures of steel slags is unknown. After EAF and ladle slag are mixed in the ratio1:1 they are supposed to react with water (water content about 10 %) to a stable, hardly permeable matrix. Nevertheless, settlements of a landfill, gases leaking out through the top cover and slope stability can represent severe problems for the liner material. Volume stability, i.e. the control of expansion during hydration, is done in all applications of hydraulic construction material.

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What is known about hydration is that the mineral phases react with water to more stable phases. However, the hydraulic properties of steel slags are in every case less than for MSWI ashes (Huber et al., 1996). One reason is the absence of organic material in steel slags. It is known from cement chemistry that the strength development during curing, i.e. setting after hydration, is the larger the longer this transformation of the minerals takes. If this knowledge is applied towards slag chemistry, a slow curing reaction would be favourable, because construction of the top cover only can take place if the slag is not hardened completely. For analysing the mineral phases, calorimetry, IR spectroscopy and XRD are suitable, but using these methods also includes some disadvantages. XRD reveals peaks in a diffractogram only if the mineral is present in a crystallized state. But the crystallinity of the hydration products of cement (Haga et al., 2002) and cementitious materials is often low. For this reason, it is common in material science to combine the XRD technique with other methods. For example, combinations with NMR, IR spectroscopy (Haga et al., 2002), SEM (Piantone et al., 2004; Shen H. et al., 2004; Murphy et al., 1997) and Differential Thermal Analysis DTA (Sharma and Pandey, 1999) have been found in the literature. Additionally, improved results of XRD analyses can be achieved if applying magnetism as with EDX (Shen H. et al., 2004, Murphy et al., 1997) to separate the sample in a low and a high magnetic fraction. Elementary analysis is of course included in all investigations as the basic method to estimate the chemical composition. About the recording of infrared bands from inorganic molecules especially from metals Smith (1999) suggests to analyze existing metals not with MID-IR but with atomic spectroscopy instruments because certain stretching and bending vibrations appear below 400 cm-1 and cannot be recorded with MID-IR. However, he states that vibrations such as C-O, N-O and S=O stretching and bending give rise to good inorganic group wave numbers in the mid-infrared. Furthermore, IR enables distinguishing minerals that have the same chemical composition but a different crystal structure (e.g. calcite and aragonite) because they cause different infrared spectra.

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Considering the limitations stated above, MID-IR spectroscopy and XRD are appropriate analytical tools for this investigation as they can complete each other. However, the interpretation of diffractograms as well as IR spectra requires experience and care. The investigations of hydration mechanism and heat release in past studies have mostly been directed towards hydration reactions of cement with blending agents. The main calorimetrical tools used for this purpose have been DTA/TGA (Haga et al., 2002; Pane and Hansen, 2005) and isothermal calorimetry (Pane and Hansen, 2005). The assessment of the stability features and the possible presence of secondary minerals as well as the attempt of predicting the aging processes occurring in a landfill liner are the main reasons for investigating steel slags. The main slag aging processes are summarized in Huber et al. (1996). With focus on ashes from municipal solid waste incineration (MSWI), the authors point out hydration, carbonation, remaining biological activity, oxidation of elementary metals, oxidation of sulphides and weathering processes as well as crystallization as the main aging processes. As materials as MSWI ashes and steel slags are alkaline, they behave as buffers for the neutralisation of acids. Huber et al. (1996) is stating the above processes leading to a decrease of buffering capacity and pH and a rise of redox potential. If the pH drops below the neutral point, leaching of certain heavy metals can occur. The prediction of a transformation of hydroxides into carbonates and - connected to a decrease of the carbonate buffer - the transformation of carbonates into bicarbonates seems to be transferable towards steel slags. Under landfill conditions these processes probably take centuries or up to thousands of years, according to some models performed about decalcification. The actual reaction time of these processes and the appearing equilibria are still unknown.

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9 CONCLUSIONS

In Europe steel slags are often landfilled or temporarily stored, although applications for their reuse already exist (e.g. as additives in a road construction). The target of nowadays research is to identify further applications for reusing steel slags and to investigate the environmental impact that steel slags would have. The conditions present in the liner have to be estimated before using alternative construction materials as steel slags.

Up to today, the long-term behaviour of steel slags is still unknown. It is affected by processes as weathering, including carbonation (carbonic acid weathering) and pH changes, leaching, aging of mineral phases and therewith stability changes of the minerals.

XRD and IR spectroscopy are suitable methods to analyse the mineral phases of steel slags. The reaction of the slags under addition of water is called hydration which has been described in this literature review. To determine the heat development and conditions of this reaction, calorimetry is a suitable technique.

XRD is applicable for determining the structure of crystalline solid samples using the diffraction angles and the intensity recorded in a diffractogram.

Infrared radiation originates from the vibration and rotation of bonds and ions of molecules. Also amorphous structures as for instance glassy mineral phases, which are common in certain steel slags, can be identified with IR spectroscopy.

With the results from these analyses, predictions of possible aging processes and the long-term behaviour can be done. The secondary phases formed during mineral aging are assumed to consist mainly of carbonates. A landfill layer of this type is expected to be stable for a long time, at least some hundred years until the carbonate buffer is used up and potentially bicarbonates form.

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10 LITERATURE CITED
Andreas, L.; Herrmann, I.; Lidstrom Larsson M.; Lagerkvist, A. (2005). Physical properties of steel slag to be reused in a landfill cover, Sardinia 2005, Tenth International Waste Management and Landfill Symposium, S. Margherita di Pula, Cagliari, Italy; 3-7 October 2005 Arm, M. (2001). Self-cementing properties of crushed demolished concrete in unbound layers: results from triaxial tests and field tests. Waste Management, Vol. 21, No. 3, p 235-239. Arm, M. (2003). Mechanical Properties of Residues as Unbound Road Materials - experimental tests on MSWI bottom ash, crushed concrete and blast furnace slag. Doctoral Thesis - KTH Stockholm, Sweden, p. 21f. Bvermann, C. (1997). Long-Term Leaching Mechanisms of Ashes and Slags: Combining Laboratory Experiments with Computer Simulations. Doctoral Thesis KTH Stockholm, Sweden, p. 12-14, 18, 28, 31 Beskow, Du Sichen (2004). Ladle glaze: major source of oxide inclusions during ladle treatment of steel. Ironmaking and Steelmaking, vol. 31 No. 5, p. 393-400. Beskow, K. et al. (2004). Impact of slag-refractory lining reactions on the formation of inclusions in steel. Ironmaking and Steelmaking, vol. 31, no. 6, p. 514f. Caley, W. F.; MacDonald, J. B. (2001). Influence of slag mineralogy on apparent viscosity in secondary steelmaking. Iron and Steelmaking, vol. 28, no. 2, p. 96- 100. Czernin W. (1964). Zementchemie fr Bauingenieure. 2nd ed. Bauverlag GmbH, Wiesbaden-Berlin, Germany, p. 12.

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Dobrowolski, J. A. (1998). Concrete Construction Handbook. 4th ed., Mc Graw-Hill Inc., New York, p.1.15, 1.17 et seq. Ecke, H., Lagerkvist, A. et al. (2003a). Carbonation of Municipal Solid Waste Incineration Fly Ash and the Impact on Metal Mobility. Journal of Environmental Engineering. ASCE / May 2003, p. 435-440. Ecke, H. (2003b). Sequestration of metals carbonated in municipal solid waste incineration (MSWI) fly ash. Waste management vol. 23, 631- 640. Euroslag (2006). Legal Status of Slags. Position Paper. January 2006. The European Slag Association EUROSLAG. Duisburg. Germany. Fllman, A-M. (1997). Charaterisation of Residues Release of contaminants from slags and ashes. Doctoral Thesis Linkping University, Sweden, p. 9. FEhS (2005). Report of the FEhS institute, no. 1/2005. Institut fr Baustoff-Forschung e.V., p. 7. Gadsden, J. A. (1975). Infrared Spectra of Minerals and Related Inorganic Compounds. London, Butterworth, p. 6 et seq., 23 et seq., 62 Glasser, F. P. (1996). Properties of cement waste composites. Waste Management, Vol. 16, Nos 1-3, pp. 159-168. Gronholz, J.; Herres, W. (1984). Understanding FT-IR Data Processing. Reprint of Dr. Alfred Huething Publishers. Grbl, P.; Weigler, H.; Karl, S. (2001). Beton-Arten, Herstellung und Eigenschaften. Ernst & Sohn Verlag fr Architektur und Technische Wissenschaften GmbH, Berlin, p. 15, 21 et seq., 28- 34, 39, 120 et seq, 128. Gnzler, H.; Gremlich, H-U. (2002). IR Spectroscopy - An Introduction. WILEY-VCH Verlag GmbH, Weinheim, Germany, p. 172 et seq.

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Gnzler, H.; Williams, A. (2001). Handbook of Analytical Techniques. Vol.1. WILEYVCH Verlag, Weinheim, Germany, p. 471 Haga, K.; Shibata, M.; Hironaga, M. (2002). Silicate Anion Structural Change in Calcium Silicate Hydrate Gel on Dissolution of Hydrated Cement. Journal of Nuclear Science and Technology, vol. 39, No. 5, p. 540-547. Herrman et al. (2005). Reuse of steel industry slags in Landfill Top Cover Constructions. Division of Waste Science and Technology, Lule University of Technology, Sweden. Hirschmann, G. (1999). Langzeitverhalten von Schlacken aus der thermischen Behandlung von Siedlungsabfllen. Fortschr. Ber. VDI Reihe 15 Nr. 220. VDI Verlag, Dsseldorf, p. 25, 60, 153, 159. Huber, H.; Jaros, M. et al. (1996). Emissionsverhalten von MVA-Schlacke nach knstlicher Alterung. Endbericht des Forschungsprojektes Alterungsverhalten von Schlacke aus der Mllverbrennung. Institut fr Abfallwirtschaft der Universitt fr Bodenkultur Wien, p. 4 et seq., 95 Jones, M. P. (1987). Applied mineralogy: A quantitative approach. London (UK), Norwell (MA/USA), Graham and Trotman Ltd, p. 104-117. Karsten, R. (1997). Bauchemie: Handbuch fr Studium und Praxis. 10th ed. C.F. Mller Verlag, Heidelberg, Germany. p. 175. Kersten, M. (1996). Emissionspotential einer Schlackenmonodeponie. Die Geowissenschaften 14/5, 180-185. Knoblauch, H.; Schneider, U. (1992). Bauchemie. Werner - Verlag GmbH, Dsseldorf, p. 126, 129 - 150. Knorr, W.; Hentschel, B. et al. (1999). Rckstnde aus der Mllverbrennung: Chancen fr eine stoffliche Verwertung von Aschen und Schlacken. Initiativen zum

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Umweltschutz, Bd 13. Deutsche Bundesstiftung Umwelt (ed.), Erich Schmidt Verlag GmbH & Co, Berlin, p. 23, 225. Koerner, R. M.; Daniel, D. E. (1997). Final covers for solid waste landfills and abandoned dumps. ASCE Press, Reston (VA), USA. p. 226 Krenkler, K. (1980). Chemie des Bauwesens. Band 1: Anorganische Chemie. SpringerVerlag, Berlin, Heidelberg, p. 160, 164, 171, 180, 182, 218. Lahl, U. (1992). Verwertung von MVA-Schlacken nach konventioneller Aufbereitung (I und II). Mll und Abfall 4, 208-216 / Mll und Abfall 9, 619-633. Marfunin, A. S. (1998). Advanced Mineralogy. Vol. 3: Mineral Matter in Space, Mantle, Ocean Floor, Biosphere, Environmental Management, and Jewelry. Springer, Berlin, Heidelberg, p. 355 Mhmel, S., Gener, W.; Mller, D. (1998). Reaktionen von Calciumaluminaten bei Hydratation und thermischer Belastung. Werkstoffwoche 98. Band VII, Symposium 9 Keramik. Heinrich, J. (ed.), Wiley-VCH, Weinheim, Germany. Mortimer, C. E. and U. Mller (2003). Chemie. Stuttgart, Thieme Verlag. p. 191f. Mostafa, N. Y.; Brown, P. W. (2005). Heat of hydration of high reactive pozzolans in blended cements: Isothermal conduction calorimetry. Thermochimica Acta 435, p. 162-167. Motz, H. and Geiseler, J. (2001). Products of steel slags as an opportunity to save natural resources. Waste Management, Vol. 21, p. 285-293. Murphy, J. N.; Meadowcroft, T. R. et al. (1997). Enhancement of the cementious properties of steelmaking slag. Canadian Metallurgical Quarterly, Vol. 36, No. 5, p. 316.

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Pane, I; Hansen, W. (2005). Investigation of blended cement and hydration by isothermal calorimetry and thermal analysis. Cement and Concrete Research, vol. 35, p. 1155-1164. Piantone, P.; Bodnan, F; Chatelet-Snidaro, L. (2004). Mineralogical study of secondary mineral phases from weathered MSWI bottom ash: implications for the modelling and trapping of heavy metals. Applied Geochemistry 19, 18911904 Rhling, S.; Eifert, H.; Kaden, R. (2000). Betonbau. Planung und Ausfhrung. Verlag Bauwesen Berlin, p. 14, 16, 20 et seq. Scheffer, F. and Schachtschabel, P. (1998). Lehrbuch der Bodenkunde. 14. Auflage. Ferdinand Enke Verlag, Stuttgart, p. 108. Sharma, R. L.; Pandey, S. P. (1999).Influence of mineral additives on the hydration characteristics of ordinary Portland cement. Cement and Concrete Research, vol. 29, p. 1525-1529. Shen, H., Forssberg, E.; Nordstrm, U. (2004). Physicochemical and minerological properties of stainless steel slags oriented to metal recovery. Resources, Conservation and Recycling 40, 245-271. Sherman Hsu (1997). Handbook of Instrumental Techniques of Analytical Chemistry. Frank Settle (Ed.). Prentice Hall PTR, Upper Saddle River, NJ, USA. p. 251. Shi, C. (2002). Characteristics and cementitious properties of ladle slag fines from steel production. Cement and Concrete Research vol. 32, p. 459-462. Shi, C.; Qian, J. (2000). High performance cementing materials from industrial slags A review. Resources, Conservation and Recycling vol. 29, p. 195-207. Smith, B. C. (1996). Fundamentals of Fourier transform infrared spectroscopy. CRC Press LLC, Boca Raton, Florida, USA, p. 89, 110.

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Smith, B. C. (1999). Infrared Spectral Interpretation - A systematic approach. CRC Press LLC, Boca Raton, Florida, USA, p. 165

Tham, G.; Andreas, L.; Lagerkvist, A. (2003) Use of ashes in landfill covers. SARDINIA 03, 9th International Waste Management and Landfill Symposium, 6-10 October 2003, S. Margherita di Pula - Cagliari (Italy), Ed.: R. Cossu and R. Stegmann, Publ. by CISA, Environmental Sanitary Engineering Centre, Italy. Tossavainen, M. (2005a). Leaching Results in the Assessment of Slag and Rock Materials as Construction Material. Doctoral Thesis - Lule University of Technology , Sweden. p. 2, 16, 19, 24 Tossavainen, M. (2005b). Characteristics of modified steel slags for use in construction. Submitted to Waste Management, May 2005. Included in Doctoral Thesis (Paper V), p. 2, 4, 12, 16. Tossavainen, M. (2005c). Leaching results of reactive materials. Submitted to Construction and Building Materials, Sept. 2005. Included in Doctoral Thesis (Paper IV), p. 18. Todorovic, J.; Ecke, H. (2005). Demobilisation of critical contaminants in four typical waste-to-energy ashes by carbonation. Submitted to Waste Management in 2005. Wenk, H.-R.; Bulakh, A. (2004). Minerals: their constitution and origin. Cambridge (UK), Cambridge University Press, p. 117-131, 550-556. Ylipekkala, J. (2005). Quality Management of Chromium Containing Steel Slags from Melt Phase to Cooling. Master Thesis, Technical University of Lule.

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Zevenbergen, C.; Van Reeuwik, L. P. et al. (1998). Weathering of MSWI bottom ash with emphasis on the glassy constituents. Journal of Geochemical exploration, vol. 62, p. 293-298.

Internet publications

[1] BlueScope Steel Limited. Internet: http://www.bluescopesteel.com/corp/navajo/display.cfm/objectID.5248A606DDF6-4E80-B74FA4A95B3F5107 Date: 2005-09-07. [2] Cement Chemistry. Cement Research Section, Dept. of Chemistry, University of Aberdeen (UK). Internet: http://www.abdn.ac.uk/chemistry/research/dem/cemhon.doc Date: 2005-11-10 [3] Huber, H.; Jaros, M.; et al.(1996). Emissionsverhalten von MVA-Schlacke nach knstlicher Alterung. Research report, Universitt fr Bodenkultur, Wien. Internet: www.wien.gv.at/ma22/pool/pdf/alterung_schlacke.pdf Date: 2005-11-10 [4] Lecture notes. Division of Building Materials and Building Technology. Katholieke Universitet Leuven (BE). Internet: http://www.kuleuven.ac.be/ Date: 2005-10-31 [5] Moosberg-Bustnes, H. Industrial by-products in the concrete industry. Swedish Cement and Concrete Institute. Internet: www.byggforsk.no/visVedlegg. aspx?vedleggID=204&dokumentID=1129 Date: 2006-01-13 [6] BMU Bundesumweltamt (Federal Ministry for the Environment, Nature Conservation and Nuclear Safety, Germany) Internet: http://www.umweltbundesamt.de/archiv/G_Eisen-u-Stahl.pdf Date: 2005-12-10

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Standards and directives

CEN EN 1744 (1998-2002). Tests for chemical properties of aggregates. EU (1975). Council Directive 1975/442/EC of 15th june 1975. Directive on Waste. The Council of the European Union, Brussels. EU (1991). Council Directive 1991/156/EC of 18th march 1991 amending Directive 1975/442/EC. The Council of the European Union, Brussels. EU (1999). Council Directive 1999/31/EC of 26th April 1999 on the Landfill of Waste. The Council of the European Union, Brussels. EU (2000). Commission Decision 2000/532/EC of 3rd may 2000. RVF (2002). Drift vid deponeringsanlggninar: Handbok, Atervinning, frbehandling och deponering (Deponiehandbok). RVF Svenska Renhallnings- verksfreningen, Malm, Sweden. SFS 2001:512 Frordning om deponering av avfall. Swedish ordinance on the landfilling of waste, Published: 2001-06-07.

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APPENDIX III

EXTENDED SUMMARY IN GERMAN Mineralphasen in Stahlschlacken beim Einsatz in der Dichtungsschicht einer Deponieoberflchenabdichtung

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Zusammenfassung
Elektroofenschlacke und Pfannenschlacke (auch Konverterschlacke genannt) sind Nebenprodukte der Stahlproduktion im Elektrolichtbogenofen und der darauf folgenden sekundrmetallurgischen Prozesse in einer sog. Pfanne. Insgesamt wurden 2004 in Europa 15, 2 Mio. Tonnen Stahlschlacken (d.h. Schlacken aus dem Sauerstoffblasverfahren, Elektroofenschlacke und Pfannenschlacke) produziert (Euroslag, 2006). Die Weiterverwendung von Stahlschlacken u. a. im Strassen-, Wasser- und Erdbau, als Dngemittel fr kalkarme Bden und als Zementzuschlagsstoff ist in einzelnen europischen Lndern sehr unterschiedlich ausgeprgt und hngt u. a. von der Verfgbarkeit natrlicher Rohstoffe ab. Die Nutzung dieser Schlacken ist dabei nicht nur von kologischem Nutzen, indem der Abbau natrlicher Rohstoffe vermieden wird, sondern auch von konomischem Vorteil, da der Bedarf an Baustoffen fr den Bau einer Deponieoberflchenabdichtung durch Deponieschlieungen in Zusammenhang mit der EU Deponierichtlinie 1999/31/EC steigen wird. Um eine Abschtzung bezglich der Verwendung von Stahlschlacken als Baumaterial in der Dichtungsschicht einer Deponie vornehmen zu knnen, bedarf es der Kenntnis ihrer physikalischen und chemischen Eigenschaften, als auch einer Einschtzung des Umwelt- und Langzeitverhaltens. Die mechanische und chemische Stabilitt einer solchen Konstruktion ist hierbei von besonderer Bedeutung. Die Ziele dieser Arbeit sind die Abschtzung der Reaktivitt der Schlacken nach erfolgter Wasserzugabe, die Bestimmung der amorphen und kristallinen Mineralphasen in den Schlacken und Mischungen aus denselbigen und die Bestimmung der Stabilitt der Hauptmineralphasen. Die mgliche Bildung neuer Minerale nach dem Mischen von Elektroofenschlacke und Pfannenschlacke unter Wasserzugabe soll ebenfalls untersucht werden. Die Reaktivitt der Schlacken nach Wasserzugabe ist zusammen mit dem zeitlichen Verlauf der Wrmeentwicklung ein Indikator fr die Bildung mehr oder weniger stabiler Mineralphasen whrend des Abbindeprozesses. Die Stabilitt der in den Stahlschlacken enthaltenen Minerale ist bedeutsam fr Mineralumwandlungen, welche unter den Bedingungen in einer Dichtungsschicht geschehen knnen. Diese Mineraltransformationen werden auch als Alterungsprozesse der Minerale bezeichnet Die sich

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bildenden sekundren Mineralphasen bestimmen die Stabilitt und das Langzeitverhalten der gesamten Oberflchenabdichtung. Eine Einschtzung zur Tauglichkeit der Analysemethoden Kalorimetrie, InfrarotSpektroskopie (IR-Spektroskopie) und Rngtendiffraktometrie (XRD) zur Beantwortung der oben genannten Fragen wurde in der Literaturstudie vorgenommen (Anhang II). Eine Methode zur Probenkrperherstellung fr die IR- and XRD-Analysen wurde entwickelt und ist in Anhang I beschrieben, zusammen mit der Probenvorbereitung der Kalorimetrieversuche und der Zusammenstellung der gesamten Messdaten. Aus der Literaturstudie geht hervor, dass Lsungskalorimetrie, XRD und IR-Spektroskopie geeignete Methoden zur Messung der Mineralphasen sowie deren Hydratation von Stahlschlacken darstellen. Die Hydratationsreaktion der Schlacken nach Wasserzugaben ist ebenfalls erlutert worden. Es soll u. a. die Wrmeentwicklung und der Verlauf der Hydratation von Elektroofenschlacke und Pfannenschlacke sowie verschiedener Schlackemischungen bestimmt werden. XRD-Analysen sind u. a. zur Strukturbestimmung fester kristalliner Proben geeignet. Die Rntgenstrahlen werden von den einzelnen Gitterebenen der Kristalle unter bestimmten Winkeln, welche die Bragg-Gleichung erfllen, gebeugt und die Intensitt der gebeugten Strahlung wird vom Detektor erfasst. Die Infrarot-Spektroskopie hingegen beruht auf Atomschwingungen in Moleklen, welche durch die einfallende Strahlung angeregt werden. Es knnen sowohl Schwingungen und Rotationen von Bindungen als auch von Ionen im Molekl detektiert werden. Gemessen wird hierbei, welcher Teil der einfallenden Infrarotstrahlung von der jeweiligen Probe absorbiert wird. Die Absorption und das dazugehrige Energieniveau im Absorptionsspektrum knnen dann der Frequenz einer Moleklschwingung zugeordnet werden. Mit Hilfe der IR-Spektroskopie knnen auch amorphe Mineralphasen gemessen werden. Amorphe Phasen knnen beispielsweise glasartige Phasen sein, welche sich aufgrund pltzlicher Abkhlung der Schlackenschmelze bilden. Der zeitliche Verlauf der Wrmeentwicklung der im Kalorimeter gemessenen Mischungen zeigte eine Aktivierung der Hydratationsreaktion durch Aluminium. Je hher der Anteil an Pfannenschlacke in der Mischung, desto grer war der gemessene

APPENDIX III

Temperaturunterschied, d.h. die abgegebene Wrmemenge. Allerdings fhrte ein grerer Anteil an Pfannenschlacke in der Mischung zu einer zeitlichen Verzgerung der maximalen Wrmefreisetzung, d. h. der maximale Reaktionsumsatz geschah spter. Die Spektroskopiemessungen ergaben, dass die nderungen in den Spektren der einzelnen Mischungen proportional zum Anteil an Elektroofenschlacke sind. Auer den Mischungen und der zwei reinen Proben von Elektroofenschlacke und Pfannenschlacke wurde zustzlich eine spektroskopische Messung von nicht hydratisierter Pfannenschlacke durchgefhrt, um dessen Spektrum mit der hydratisierten Schlackenform vergleichen zu knnen. Mithilfe einer qualitativen Analyse der Spektren wurden Absorptionsbanden von anorganischen Karbonaten, Kalziumsilikaten und Aluminiumoxid identifiziert. Der grte Unterschied zwischen allen Proben befand sich in der Wellenzahl-Region von 3500-3200 cm-1. Die gemessene Probe aus 100 % (hydratisierter) Pfannenschlacke zeigte deutliche Absorptionsbanden in diesem Bereich, wohingegen dies bei Elektroofenschlacke und nicht hydratisierter Pfannenschlacke nicht der Fall war. In dem genannten Wellenzahl-Bereich absorbieren O-H Bindungen die einfallende Strahlung. Durch die Absorptionsmessung dieser Bindungen konnte der Einbau und die Absorption von Wassermoleklen in die Mineralstruktur durch Hydratation nachgewiesen werden. Diese Absorptionsbanden sind also nur bei einer entsprechend ausgeprgten Hydratation erkennbar. Das hydraulische Verhalten wird vor allem durch chemischen und mineralogischen Eigenschaften bestimmt. Mit der Methode der Rntgenbeugung wurden die Hauptphasen aller Schlackeproben inklusive der Schlackenmischungen gemessen. Dabei ergab sich, dass die Schlackemischungen die gleichen Minerale wie reine Pfannen- bzw. Elektroofenschlacke besaen. Es konnten keine Mineralneubildungen bei den Mischungen gemessen werden. Dies kann zum einen daran liegen, dass es keine Neubildungen von Mineralphasen gab. Es kann aber auch am Messgert liegen, welches eine Phase nur detektiert, wenn sie mehr als 4 wt-% am Anteil der Gesamtprobe betrgt. Die Hauptminerale von Pfannenschlacke sind - Dikalziumsilikat ( - Ca2SiO4) und Mayenit. Bei Elektroofenschlacke sind Merwinit und Monticellit am hufigsten vertreten. Diese Ergebnisse beruhen auf thermodynamischen Modellen. Beide Schlacken bestehen

APPENDIX III

vorwiegend aus kristallinen Phasen. Dies lsst sich mit der langsamen Abkhlung der Schlackenschmelze im Stahlwerk erklren. Eine Schlussfolgerung hinsichtlich einer Korrelation zwischen Abbindeverhalten und Mineralphasen ist nur begrenzt mglich. Bestimmte Mineralphasen wie Dikalziumsilikat besitzen nur geringe hydraulische Eigenschaften. Deren Hydratation und Abbindeverhalten wird entsprechend gering ausfallen. Es herrscht keine Korrelation zwischen Hydratationswrmefreisetzung und Stabilitt einer bestimmten Mineralphase. Es kann somit Phasen geben, die bei hoher Wrmefreisetzung geringe Endfestigkeiten nach dem Abbinden entwickeln. Da Pfannenschlacke einen Beitrag zur Hydratationsreaktion liefert, da mehr reaktives Kalziumoxid vorhanden ist und Elektroofenschlacke die Festigkeiten der Mischungen positiv beeinflusst, wird eine Mischung beider Schlacken zu gleichen Anteilen in der Dichtungsschicht einer Deponieoberflchenabdichtung als optimal angesehen. Das Langzeitverhalten der Schlacken ist zurzeit noch nicht bekannt und kann daher nur abgeschtzt werden. Es wird durch Faktoren wie Verwitterung (eingeschlossen darin ist die Karbonatisierung), Feuchtigkeit, pH Vernderungen und Redoxpotential sowie die Pufferkapazitt der Minerale beeinflusst. Die Karbonatisierung wird dabei vor allem vom CO2 - Gehalt und der Feuchtigkeit beieinflusst. Aufgrund der Literaturrecherche und Beobachtungen an den Probekrper nach einer dreimonatigen Lagerungszeit wird angenommen, dass die sich bildenden sekundren Phasen aus Stahlschlacken vor allem aus Karbonaten bestehen. Allerdings werden nicht alle Mineralphasen verwittern und sekundre Phasen bilden. Nach hinreichend langen Zeitrumen von mehreren Tausend Jahren knnen sich ebenfalls Hydrogenkarbonate bilden, allerdings muss die Pufferkapazitt der Schlackeschicht aus Karbonaten vorher hinreichend gesunken sein. Forschungsbedarf ist vor allem im Bereich der Schlackealterung whrend verschiedener Lagerungsbedingungen und der thermodynamischen Eigenschaften der Minerale zu sehen. Experimente und Modelle zur Vorhersage von chemischen und strukturellen Vernderungen der Minerale knnen hier einen Betrag zur Klrung des Langzeitverhaltens liefern. Bei experimentellen Versuchen wird versucht diese Langzeitprozesse knstlich zu beschleunigen. Diese Forschungen sind unerlsslich, um Stahlschlacken Baumaterial einsetzen zu knnen.

Eidesstattliche Erklrung Hiermit erklre ich an Eides statt, dass ich die vorliegende Arbeit selbststndig und ohne fremde Hilfe angefertigt habe. Smtliche benutzten Informationsquellen sowie das Gedankengut Dritter wurden im Text als solche kenntlich gemacht und im Literaturverzeichnis angefhrt. Die Arbeit wurde bisher nicht verffentlicht und keiner Prfungsbehrde vorgelegt.

Dresden, den 21. Mrz 2006