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CHEMICAL INTERACTIONS IN CALCIUM ALUMINATE CEMENT (CAC) BASED CASTABLES CONTAINING M AGNESIA
by Thomas A. Bier, Christopher Parr, Catherine Revais, Herv Fryda presented at the UNITECR congress; 1997.

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Abstract
Castables based on Alumina and CAC which contain Magnesia form Al2O3.MgO spinels which have the potential to enhance performance. The principal applications are within Steel Ladles in areas such as impact zones. Numerous papers have been published which show the potential of these castables via investigations into phase formation during heating, expansion and strength development. It is these properties that will largely determine the performance of these castables within the environment of the steel ladle. This paper investigates the role of admixtures and amorphous silica with respect to their chemical interactions with the reactive MgO. Correlations to rheological behavior will be shown. A simple model of interactions between reactive components in such systems will be proposed.

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Introduction

Calcium Aluminate Cement (CAC)

The development to use castables in ladle lining has led to refractory concretes which contain in the fired state spinel in order to resist the severe attacks in a ladle thus being competitive to bricks. This can be achieved by two approaches : (a) including synthetic spinel as aggregate in an alumina castable1 or (b) including MgO to the binder phase of the castable, which will form during heat up with the reactive alumina present, Al2O3.MgO spinel. The second approach seems to give more resistant concretes in specific applications 2 and is certainly less costly than the spinel aggregate solution. Numerous papers 3,4,5 have been published in recent years relating to the resistance to slag attack, expansion behaviour and thermodynamic stability of spinel containing castables. There are however few published studies relating to the rheological behaviour and hardening kinetics of such systems. It is well known that for spinel forming castables the inclusion of MgO disturbs the workability of a concrete. First results on workability have been presented in 6 focusing on flow decay curves for a MgO containing ULCC laboratory formulation. Some results comparing workability of spinel containing versus MgO containing spinel forming castables have been shown in 7, 8. In the following chapters results are shown on chemical interactions in spinel forming systems. Figure 1 shows a sketch of the active ingredients when looking at spinel forming castables.

Admixtures

Silica Fume

Fine, reactive alumina

MgO

Figure 1. Active ingredients for spinel forming castables

Normally we have interactions between four mineral phases controlled by admixtures to give the desired placing properties and green strengths. For spinel forming and the performance of the resulting concrete only fine alumina, MgO and their respective physico-chemical properties are relevant. Silica fume plays according to most refractory researchers a twofold role : - Influence on MgO reactivity; anti-slaking agent. - Mitigation of volume expansion due to spinel formation.

Experimental approach

Formulations investigated The experiments conducted are based on a simple formulation of a ULCC castable containing Magnesia (MgO) in order to form Al2O3.MgO spinels upon firing. Some comparative tests have been carried out on the formulation without MgO addition. This formulation has been optimised where particle size distribution and spinel forming properties are concerned. The binder phase of the formulation is given in Table I. Figure 1 shows the particle size distribution used for the tabular alumina aggregates and active fine components.

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% Passing 100 q = 0,28 10 q = 0,39

Experimental methods used

1 1 10 Particle size 100 (microns) 1000 10000

Figure 2. Particle size distribution of formulation Table I. Binder composition Active (fine) material (%) Type of Elkem MgO Alumina Secar formulation 971U 152SV 71 with MgO 2 5 8 2 without MgO 5 0 13 2

Investigations on Concretes Working time and flow value have been determined with the ASTM cone (100 mm base , 70 mm top and 80 mm height) on a vibrating table. The flow values have been determined for a 20 second vibration time directly after mixing and after 15, 30, 45 and 60 min. They are expressed in mm and represent the diameter of the cake reached after vibration of the cone. The working time represents the time at the end of which no flow on the vibrating table can be achieved. Heat profiles The heat produced by exothermic reactions within the concrete has been measured as a function of time. The concrete has been placed in insulated (styrofoam) beaker and a thermocouple stuck into the concrete. Investigations on binder phase Calorimetry and rheological profiles have been measured for the binder phases, consisting of the composition given in Table I and the -325 mesh part of the tabular alumina aggregate. A detailed description of the method and its application on castables is being presented in 9. Calorimetry After mixing, the binder is placed into the cell of a calorimeter which has been specially developed to measure the heat after mixing. Heat flow is associated with a chemical reaction occurring within the binder. Heat flow has been reported by others workers to be representative of castables properties10. Rheometry After mixing, the binder is placed into a rheometer. The rheometer (Contrives, Rheomat 115A) is normally composed of two coaxial cylinders, the binder being placed within the narrow space between the cylinders. In the present experiment, the inner cylinder was replaced by a special blade. The binder is placed within the outer cylinder after mixing. The

Water 5,5 5,5

Admixture packages and MgO fineness have been varied in order to influence setting behaviour (Working Time). The impact of these variations as well as the presence of MgO have been studied with various methods. Two different admixtures or admixture packages have been used: Sodium polyphosphate (TPP) and a combination of Darvan 7S, citric acid (CT) and sodium carbonate. The fineness of the MgO has been varied by combining the 5% of MgO in the formula out of two differently ground MgO's as shown in Table II.
Table II. MgO compositions for formulations tested MgO use for castable (%) Raw material % Coarse Medium Fine MgO MgO MgO MgO N < 0,4 mm 5 2,5 0 MgO N < 0,2 mm 0 2,5 5

For the formulation with the medium MgO the admixtures were adjusted in such a way as to obtain a working of 60 minutes. These admixtures additions were then also applied with the coarse and fine MgO formulations.

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propeller is rotated every 15 minutes at 5 rpm during 10 seconds, and the momentum necessary is monitored. The result of the experiment is a value of the momentum every 15 minutes. An increase of the momentum is associated with a stiffening of the binder.

Results

Tests on concretes Results for flow decay and working times obtained are given in Table III for five castables.
Table III. Flow values and working times measured on concretes Formulation min 0 Fine MgO MgO - 0,06% TPP MgO - package Coarse MgO MgO - 0,06% TPP MgO - package Without MgO MgO - 0,06% TPP 245 260 254 265 275 Flow value in mm after min 15 min 30 min 45 220 247 238 205 229 224 244 146 193 182 299 min 60 0 130 173 Working time min 50 60 60 80 420

Package = 0,05% Darvan 7S / 0,01% Citric Acid, 1H20 / 0,005% Na2CO3

The values obtained for the castables containing MgO are very close to results reported in 6, where also results on the formulations with the medium MgO grading are shown. In order to better compare only formulations with either coarse or five MgO are treated in this paper. The major effects shown here are : - Fine MgO reduces flow value and working time. - An additive combination allows to optimize flow behavior with respect to a monoadditive formula. In order to demonstrate the influence of MgO and decreased silica fume the last line shows results from the ULCC formulation. The flow value and working time for the formulation is higher and especially the working time with 420 minutes is

much longer for the ULCC formulation without MgO. Tests on binder phase of castables Figure 3 shows rheometry curves for the binder phases of the formulations shown above. The momentum is given as a function of time for a measurement every 15 minutes.
45 40
Momentum (mNm)

35 30 25 20 15 10 5 0 15 30 45 60 Time (min) 75 90 105

Coarse MgO - T PP Coarse MgO - Package Fine MgO - TPP Fine MgO - Package ULCC w/o MgO

Figure 3. Rheology: Momentum as a function of time for the five different binder phases

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Low momentum indicates that the material is still workable that is to say that no structuring due to hydration has occurred yet. Once hydration or even partial hydration starts, the material acquires a certain structure and stiffens, represented by an increase in momentum. The curves shown are in good agreement with the working times measured on the concretes, representing the whole formulation. These working times are given in the diagram for the corresponding formulations. Also, the ULCC formulation without MgO does not show any structuring at all within the time scale looked at in the diagram. Figure 4 shows calorimetry curves for the five binder phases investigated. The heat flow is given as a function of time. Similar effects have been measured by monitoring heat profiles on the concretes.
mw/g 1 0,8 0,6 0,4 0,2 0 -0,2 -0,4 -0,6 -0,8 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 min

It indicates by its exothermic character that a chemical reaction occurs even if it might be, quantitatively, a weak reaction. This reaction seems to be influenced by admixtures, active fillers and CAC. For the ULCC formulation investigated the addition of MgO seems to provoke or strengthen this peak. The time the peak occurs seems to be controlled by the admixtures used because we can clearly distinguish two sets of peaks representing the formulations with TPP and with the admixture package, respectively. The admixture package causes an earlier peak pi than the use of TPP in the formulation. A similar effect has also been seen in earlier investigations where conductimetry has been used to characterize the effect of admixtures in refractory castables 11,12. TPP shows also as a very strong retardation of the dissolution step. This strong retardation of dissolution would be in accordance with a later appearance of pi with respect to the use of the admixture package. For the massive precipitation the effect is reversed. The massive precipitation for formulations with the admixture package occurs at about 2000 minutes and is not given in the diagram. TPP as an admixture allows an earlier massive precipitation than the use of the admixture package. This is confirmed by higher green strenghts after 36 hours. The castables with fine MgO and TPP exhibits 8,7 MPa as compared to 4,6 MPa for the use of the admixture package. However, the fineness of the MgO does not play any role on the time when the peak Pi occurs. On the other hand the flow decay curves observed in 6 and also presented in Table III and the rheometry (Figure 3) show an influence of MgO fineness and admixtures. This means also that despite the potential of a disturbance (decay) of flow by an early reaction we do not find any general correlation between the time of the peak Pi and a rheological parameter such as working time or increase in momentum. In 9 correlation

Package, pi TPP, pi massive precipitation

Coarse MgO Fine

ULCC w/o MgO

Figure 4. Calorimetry curves for the binder phases of the five formulations

The system without MgO shows a curve with a behavior close to a pure cement hydration. Three phases can be distinguished: dissolution or wetting, dormant period and massive precipitation which are classical for the hydration of a cementitious material. When looking at the systems containing MgO an additional peak pi can be observed. This peak is not present in the ULCC formulation without MgO or cannot be detected. This peak, occurring also in other refractory LCC formulations is being described in more detail in 9.

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are shown but only within a given, well defined system. These results combined (calorimetry and rheometry) clearly demonstrate that we have to investigate further concentrating in distinguishing and monitoring at least two different chemical mechanisms: - Interactions (formation of hydrates) which can be detected by calorimetry, conductivity or LOI. - Topochemical interactions modifying surface charges which influence the forces of defloculation, hence the structuring of the paste and eventually the rheological behavior.

2H.

Naaby, O. Abildgaard, G. Stallmann, C. Whrmeyer und J. Meidell, "Refractory wear mechanisms and influence on metallurgy and steel quality as a result of the conversion to endless lining at Det Danske Stalvalsevaerk", XXXVII Refractory Colloquium, October 1994, Aachen, Germany.
3A.

Sainz, A. Mazzoni, E. Aglietti and A. Caballero, "Thermochemical formation and stability of spinel (MgO.Al2O3 ) under strongly reduction conditions", UNITECR '95.
4Zenbe-e

Conclusions

Nakagawa, Naoya Enomoto, In-Suk Yi, and Keisuke Asano, "Effect of Corundum/periclase sizes on expansion behavior during synthesis of spinel.", UNITECR '95.
5M.

Spinel forming castables contain MgO and are difficult to formulate not only what high temperature properties are concerned but also with respect to master placing properties. Results from our study show that : - The presence of MgO disturbs working time. - The fineness of MgO influences working time; fine MgO yields shorter working times than coarse MgO. - Admixtures are necessary to master rheological properties of MgO containing formulations. - Admixture combinations are more efficient than a mono-admixture approach. - MgO reacts with admixtures and fillers, modifies the thermal profile and hence the hydration. - The exact nature of these reactions and their impact on rheology are not known yet.

Rigaud, S. Palco, Ning Wang, "Spinel formation in the MgO-Al2O3 system relevant to basic castables", UNITECR '95.
6Th.A.

Bier et al, "Workability of Calcium Aluminates Cement based castables containing magnesia", ALAFAR 1996.
7Ch.

Alt, T.A. Bier, N.E. Bunt and C. Parr, "Comparison of the effects of workability on spinel containing and spinel forming castables", American Ceramic Society , 1997.
8Th.A.

Bier, C. Parr, C. Revais, "Formulation logics in Spinel Castables", ALAFAR 1997.

9H.

Fryda et al, "Relation between setting properties of Low Cement Castables and interactions within the binder system (CACFillers-Admixtures-Water)", UNITECR '97.
10R.

6
1T.

References

Krebs, "Demands on unshaped refractories in the next decade", UNITECR '95, 2, pp 253-261, 1995.
11T.A.

Kanatani, Y. Imaiida, "Application of an alumina-spinel castable to the teeming ladle for stainless steelmaking", UNITECR '93.

Bier, A. Mathieu, B. Espinosa, J.P. Bayoux, "The use of conductimetry to characterize the reactivity of high alumina cements", UNITECR '93.

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12T.A.

Bier, C. Parr, "Admixtures with calcium aluminate cements and CAC based castables", 28th Annual SA Ceramic Society Symposium, Johannesburg, Republic of South Africa, 1996.

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