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THE ROLES OF FINE SILICA AND REACTIVE ALUMINA AND THEIR INTERACTIONS WITH CALCIUM ALUMINATES IN REFRACTORY CASTABLES
by Thomas A. Bier, Christopher Parr, Catherine Revais, Akihiko Namba presented at the TARJ, Tokyo, Japan; 1998.

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Abstract
Fine, amorphous silica plays an important role in modern castable technology. Though potentially negative for hot strength, it largely improves placing characteristics and reduces the water demand. Many works have been published on the physical aspects such as particle size distribution and the impact on placing properties as well as on hot properties of castables containing silica fume. The chemical aspects that become very important with respect to interaction with CAC and admixtures have mostly been studied in diluted suspensions. This paper reviews results of chemical interactions in suspensions. It presents results on various castables with and without silica on placing characteristics such as flow values. For the same castables hot properties have been determined. The castables investigated represent the major applications of today. The results are discussed with respect to macroscopic properties on placing and hot strength.

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Introduction
Flow (%) Strength (Mpa) Flow value necessary for placing Flow decay (time) WT Shortly after WT

Modern castable technology relies on the mastering of interactions between cement, additives and fine fillers in order to achieve the desired performances. In simplifying we can look at two groups of performances: - The placing and setting characteristics ; - The behavior during heat up, at high temperature and cool down. For placing and setting the following sketch (Figure 1) shows an ideal behavior. The temperature behavior depends largely on the chosen application but demanding applications such as ladle-linings ask for high hot strengths,
Table I. Typical properties for ladle castables Property HMOR Mpa Porosity % at 1000C at 1400C after 1000C after 1400C MgO 6,5 4 24,8 20,2

Final set (demolding) Initial set

Figure 1. Transition from flow to strength for a castable

low porosity and high corrosion resistance. Typical values for different castables according to /1/ are given in Table I.

MgO/SiO2 10 2 24,1 20,0

Spinel (Sp) 8,5 1,5 21 20,6

Sp/SiO2 6,5 6 22,5 20,6

* All values approximate taken from graphs

As indicated before, in most cases, these performances can only be achieved by the combination of a hydraulic binder e.g. Calcium Aluminate Cement (CAC) or Reactive Alumina (RA). This composite binder or base will mostly determine the final performance. In order to achieve the final performance and to be able to place the castable, admixtures are necessary for controlling the mutual interaction between the components of the base. The concept of admixtures use and their functions are been described in /2, 3/. This paper will deal with the role of fine fillers. Silica fume (SF) can be considered as the filler which allowed a breakthrough in castable technology. It allows by its fineness a particle size distribution very favorable to flow behavior /4/ reduces water demand and hence final porosity.

At the same time impressive strength values can be obtained. The same technology is also used for the so called DSP materials (Densified by Small Particles) where the combination of SF with Portland cement allows strength values exceeding 100 Mpa /5/. Upon heat up, SF can form Gehlinite, a mineral that melts at moderate temperatures (1250C) and which allows to compensate for a volume expansion, but also can diminish the final strength. Fine alumina does not necessarily improve placing characteristics because it has to be deflocculated itself by admixtures which explains the difficulties to achieve good placing characteristics in alumina castables without any silica fume. On the other hand hot properties are largely improved because the formulation of alumina rich phases such as CA6 or MA-spinel is encouraged.

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2
2.1.

Experimental approach
Raw materials and formulations 2.1.2. Formulations Low Cement Castables (LCC) have been investigated where spinel castable represents silica fume free castable. The mix-designs of three formulations are given in Table III.

2.1.1. Basic approach Chemical interactions between CAC, Admixtures and SF and RA, respectively, have been investigated either in diluted systems, suspensions with water/solid ratios of 5 or 10, or in pastes imitating the binder phase and containing raw materials smaller than 80 mm/6/. All raw materials used, also for the full formulations in chapter 2.1.2, are given in Table II.
Table II. Raw materials used for the study Tabular Alumina Spinel Reactive Alumina Silica fume Cement Additives

Standard Tabular Alumina Al-Mg spinel 3 different aluminas 3 different silica fume 70% Al2O and 80% Al2O3 CAC Dispersants: Sodium tripoly phosphate (TPP), Sodium hexa-metaphosphate (HMP), Polyacrylate (D7S), Polyglycol (Cast) Retarders: Boric acid (BA) Accelerators: Lithium carbonate, sodium carbonate (SC) Table III. Comparison of the formulations used Tabular Alumina (mesh) 6 10 -8 8 14 14 28 - 48 0,5 1 0,5 0 0,045 System 1 33 16 6 5 9 4 10 7 10 5 System 2 33 16 6 5 9 4 10 11 6 5 System 3 22 10 19 29 5 10 5 5

Spinel (mm)

Silica fume Reactive alumina 70% CAC 80% CAC Water

The particle size distributions are given as a loglog plot in Figure 2. The target distributions were calculated according to the Andreasen model with a distribution modulus of 0,22. This would provide a compromise between optimum dense particle packing and ideal placing characteristics. We see

quite clearly that the presence of silica fume changes the particle size distribution significantly through the addition of ultra fines. Using ultra fine alumina alone it is not possible to exactly match the ideal curve.

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% passing 100 System 2 System 3

(II) the dormant period which corresponds to placing (III) the massive precipitation which corresponds to set and strength development 2.2.2. Testing of castables Placing Figure 4 shows the placing characteristics that have been measured flow value, working time and flow decay.
Experiment 70 mm 50 mm d0 = 100 mm d1

10

1 0,1 1 10 100 1000 10000 100000 particle size (microns)

Figure 2. Andreasen diagrams comparing particle size distributions between System 2 and 3

2.2.

Testing

2.2.1. Basic tests In order to understand the nature of interactions conductivity of stirred suspensions and microcalorimetry have been employed. Figure 3 shows the two parameters as a function of time for a CAC paste hydration.

Result Flow value Decay

Time Working time

Figure 4. Flow value, flow decay and working time

I Conductivity (mS/cm) or Heat flow (mW/g)

II

III

Flow value

time dissolution dormant period massive precipitation

The flow value has been determined using a cone with 100-mm base diameter, 50 mm high and 70mm top diameter. The cone is placed on a vibrating or shock table (ASTM 230C), filled with the castable, then taken away and after 25 blows (shock table) or 20 seconds of vibration the diameter of the resulting "cake" is measured and considered as the flow value in mm. To express the flow value in percent we calculate: FV [%] = cake diameter - initial diameter initial diameter
Working time

Figure 3. Examples for conductivity and calorimetry curves.

As it has been described before /3,6,7/ we can clearly distinguish three phases: (I) the dissolution phase which corresponds to mixing

100

The time after which the initial cone would not flow at all under vibration is called working time.

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Flow decay

3.1.

Basic systems

Flow values measured as a function of time and displayed as a curve show with which speed an initial flow decays or can be maintained.
Hot properties

The hot state and the properties of the ceramised material, respectively, have been evaluated by the following measures: - After firing to 1200C and 1500C with 5 hours soak time: density, porosity, volume change. - At temperature after soak: hot moduli of rupture, creep behavior.

The interactions of silica fume and CAC during hydration has been shown with conductivity in /3/ where a strong retardation of the dissolution mechanism is demonstrated by a rupture in form of a small plateau during the initial, rapid increase of conductivity. Recent results /8/ with calorimetry also show that silica fume modifies the hydration behavior of a CAC cement. Figure 5 demonstrates this effect for the interaction of various silica fumes with mono-calcium aluminate CA. For CA2 this effect does not seem to be present.

Results

Figure 5. Heat flow curves for three different silica fumes with CA

In the presence of silica fume an additional peak occurs indicating an early reaction according to Gener probably on the surface. For alumina a rather physico-chemical adsorption reaction modifying the calcium to alumina ratio (C/A) in the solution seems to be the major influence /9/. In this logic the specific surface area and particle size of the used reactive alumina plays a major role. Besides the direct influence of alumina, the soluble alkalis often have a more pronounced effect on workability /10/.

3.2.

Castables

3.2.1. Behavior during placing Table IV shows placing characteristics for castables from System 1 through System 3 at an equal water demand of 5% but with different admixture systems. What the fine fillers are concerned placing is mostly influenced by silica fume. This means that a system containing silica fume can achieve good performances with relatively simple monoadmixture systems such as TPP or HMP.

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Table IV. Placing characteristics for the castables used ASTM flow at 20 min 30 min 45 min 60 min System 1 120 170 145 135 115 70 HMP BA System 2 159 213 120 200 190 180 35 135 D7S Cast BA Li2CO3 SC System 3 222 213 210 195 88 HMP only

Working time Admixture system

43 No

ASTM Flow Value (mm)

If no silica fume is present, the placing characteristics are fairly poor (80% CAC) as we can see for System 1 where no additional admixtures have been used. In this case it is difficult to use additional admixtures because a CAC with 80% alumina contains already admixtures. For a 70% CAC we can much more easily use admixtures as we did for System 2. These results show that we have to use in any case at least two or three admixtures to approach performances as obtained by only HMP in a SF containing castable. The values given for System 2 depend also on the additional alumina used. Therefore tests have also to be performed in order to find the optimal admixtures combination for given mineral raw materials. The results obtained for System 1 and 2 containing spinel hold also true for pure alumina LCC or ULCC formulation. Figure 6 demonstrates this effect even more clearly. ASTM flow decay curves are given for several systems. The seven systems presented correspond to those of Table IV with the addition of two systems using HMP and BA as admixtures and different aluminas (see also legend Figure 6). In this experiment we observe again the best flow behavior for a silica fume containing formulation and little flow beyond 20-30 minutes for the 80% CAC formulation.

250 200 150 100 50 0 20 30 45 Time (min) 60

Serie Serie Serie Serie Serie Serie Serie 1: 80% CAC 2: HMP + Al1 3: HMP + Al2 4: HMP + Al3 5: D7S + Al3 6: CAST + Al3 7: HMP + SF

Figure 6. Flow decay curves for compositions.

various castable

Table V gives the characteristics of the different reactive aluminas used.

Table V. Typical properties BET (m2/g) Al1 Al2 Al3 3,3 3,0 7,0

D50 (micron) 1,5 2,2 0,6 0;8

Na2O (%) 0,03 0,06 0,08

For the use of HMP the same initial flow is reached but depending on the alumina used a more or less rapid decay will follow. In our case the polyacrylate did not improve flow, even when used within a triple admixture package. The polyglycol shows a flow behavior very close to the flow obtained in presence of silica fume. The tendency to extend working times to much is counterbalanced by the use of Li2CO3.

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3.2.2. Behavior at temperature Figure 7 shows the hot moduli of rupture at 1200C and 1500C for the seven series presented already in Figure 6.
3,25 3,2 3,15 3,1 3,05 3 2,95 2,9 2,85 1 2 3 4 5 6 7 20 18 16 14 12 10 8 6 4 2 0 Density after 1200C Density after 1500C Porosity after 1200C Porosity after 1500C

Density (cm3/g)

Porosity (%)

30
HMOR (MPa)

25 20 15 10 5 0 1 2 3 4 5 6 7 1200C 1500C

Figure 8. Porosities and densities after firing to 1200C and 1500C, respectively

Figure 7. Hot modulus of rupture for the castables investigated

Permanent Volume Change (%)

At 1200C all HMOR are between 8 and 13 MPa except the SF containing castable which attains 16 MPa. At 1500C castables with mediocre flow values tend to exhibit much better strengths (HMOR > 20 MPa) than those castables with a very good flow behavior. This could be related to the fact that the water demand has been equal for all samples independent of the admixture used. If we mix the castable number 6 with a lower water amount of 3,7% we achieve excellent HMOR superior to 20 MPa as for the other mixes shown. At the same time a low porosity (14,7%) is achieved and the high temperature creep does not start below 1650C. Porosity and densities are given in Figure 8 for the seven castables investigated.

Major differences are only visible between castables n 1 and n 7. The densities go up considerably when increasing the firing temperature from 1200C to 1500C. However, the porosity stays the same for n 1 but decreases largely for n 7 which shows an effect of melting confirmed by low HMOR at 1500C (Figure 7) and a high temperature creep beginning already at 1314C and exceeding 5% at 1650C, the maximum temperature tested. The permanent volume change after different firing temperatures is given for the seven castables tested in Figure 9.

1 0,5 0 -0,5 -1 -1,5 1 2 3 4 5 6 7 1200 C 1500 C

Figure 9. Permanent volume change after firing to 1200C and 1500C, respectively

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Two points are worthwhile mentioning. The castable with silica fume shows besides low porosity, low HMOR, high creep at temperature also a very high permanent shrinkage exceeding 1,2%. This confirms that for this given castable 1500C are definitively above the desired service temperature. The castable n 3 with alumina n 2 shows at 1500C an expansion which we cannot yet explain but which would be somewhat in line with the fact that amongst the HMP admixture examples the Al2 type shows the lowest HMOR at 1500C, highest porosity and lowest density.

This means that we are looking at the interaction CAC-alumina-admixtures. For the placing characteristics most data are available but their exact influence on strength especially hot strength is not totally understood yet and should be subject to future research.

5
/1/

References

Conclusions

The results presented show quite clearly that there is no real replacement for silica fume where placing properties are concerned. This filler plays a special role through its particle size but also through chemical interactions within the refractory castables that enables a simple admixture system to be efficient. The preferred mono admixtures are either TPP or HMP. Without silica fume either complex admixture combinations or new generation plasticisers have to be employed in order to achieve very good flow behavior because alumina is more difficult to deffloculate. The origin of the alumina source plays also a role. For castables with very good initial flow values and little decay as a function of time the working times tend to become very long. In these combinations an accelerator is necessary to control working time. Upon heat-up and at high temperatures exceeding 1300C the alumina system exhibits considerable hot strength. The level of these strength values depends on the reactive aluminas used as well as on the admixtures employed to control placing of the castables. The influence that plays an even more important role is the porosity determined by the water demand of the system.

M. Nanba, T. Kaneshige, Y. Hamazaki, H. Nishio and I. Ebizawa; Thermal Characteristics of Castables for Teeming Ladle; Taikabutsu Overseas, Vol. 16 No.3. /2/ Th.A. Bier, Ch. Parr; Admixtures with Calcium Aluminate Cement and CAC based castables; R.S.A., 1996. /3/ Th.A. Bier, A. Mathieu, B. Espinosa, J.P. Bayoux; The use of conductimetry to characterize the reactivity of high alumina cements; UNITECR 93, Brazil, 1993. /4/ B. Myhre, A.M. Hundere; The use of particle size distribution in development of refractory castables; ALAFAR, Argentina, 1996. /5/ H.H. Bache; Densified Cement Ultra-Fine Particle based materials; Second Intl Conference on Superplasticizers in Concrete; Canada, 1981. /6/ H. Fryda, C. Revais, Th. Bier, Ch. Parr; Chemical interactions in Calcium Aluminate Cement (CAC) based castables containing magnesia; UNITECR 97, New Orleans, 1997. /7/ H.J. Kuzel and H. Baier; Hydration of calcium aluminate cements in the presence of calcium carbonate; Eur. J. Mineral, 1996, 8, 129-141. /8/ Report Gener et al; Behavior of CA/CA2cements during thermal treatment; Report n 9, not published. /9/ A. Mathieu, A. Capmas, J.P. Bayoux and D. Richon; Calcium aluminate cement and reactive alumina; UNITECR 93, Brazil, 1993. /10/ A.Rettel; Hydratation des CA et des mlanges CA + Alumines; Internal Report; LCR, 1995.

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