Technical Paper

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CALCIUM

ALUMINATE

CEMENTS

FOR

REFRACTORY

GUNNING

APPLICATIONS

by Christopher Parr, Catherine Revais, Thomas A. Bier presented at The Third International Symposium on Refractories, Beijing, China; 1998.

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Abstract
This paper will present the results of an investigation in the application of Calcium Aluminate Cements (CAC) for refractory gunning products to determine the relationships between cement behaviour and gunning performance. Three CAC's are evaluated in a variety of model formulations. Properties studied include gunning parameters and characteristics along with the resultant properties of gunned samples. A parallel laboratory investigation into the cement characteristics is presented and conclusions are drawn between cement characteristics and actual gunning performance.

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Introduction

Experimental approach

The development of monolithic refractories based upon calcium aluminate bonding systems can be considered to have followed two axes in recent years1,2. The first being an improvement in ultimate performance through the application of lower cement content deflocculated castables. This however was largely at the expensive of installation flexibility and often resulted in products which had a high degree of installation sensitivity. The second and more recent development axe has been the move towards products with improved installation performance whilst still retaining the inherent performance advantages realised by the first evolution. This development has been related to both casting installation techniques 3,4 as well as gunning techniques 5,6. More recent developments with gunning installations have focussed upon both the wet or semi-wet gunning techniques 7 as well as the more traditional dry gunning technique8. It is clear that9 further development and optimisation of these products will continue. However the dry gunning technique still offers many inherent advantages 8 such as its simplicity, quick set up time and ease of use. This is evidenced today by the relatively large quantities of product still installed by this technique in a wide variety of application areas. The disadvantages of the dry technique are well known and are primarily related to dusting and rebound losses. This paper investigates these dry gunning mixes and attempts to identify some of the parameters that influence the gunning performance of calcium aluminate based compositions. The objective is to optimise the levers which lead to mixes with low rebound and dusting whilst still retaining good physical properties in the as gunned state.

Materials used The program was designed to evaluate the behaviour of three calcium aluminate cement types along with a selection of additives which would function as rheology modifiers in model formulations based upon a chamotte aggregate. The chemical composition of the main raw materials used are shown in Table 1. From these base materials model formulations were constructed (Table 2). A small clay addition was made to these base formulations to provide sufficient plasticity. Three additive types were considered, an increased clay addition, Lithium Carbonate and R1001 a calcium aluminate with a reactive mineral phase. For each of these base formulations three different cements were used; a 50% alumina cement Secar 51BTF, a 70% alumina cement Secar 71 and an 80% alumina cement Secar 80. The particle size distributions were optimised using the Dinger and Funk model10 with a distribution modulus of 0,2. This value was chosen as previous experimental evidence had shown this to be optimum for gunning performance. The actual particle size distribution achieved compared to the target is shown in Graph 1.

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Table 1. Chemical composition of raw materials : % Chamotte Clay Secar 51BTF Secar 71 Secar 80 R1001 Table 2. Base formulations RAW MATERIAL BASE COMPONENTS Chamotte: 40/42% Chamotte: 40/42% Chamotte: 40/42% Chamotte: 40/42% Plastic Clay: Puraflo RA Secar cement ADDITIVES Puraflo RA Lithium carbonate R1001

Al2O3 41,00 25,00 54,01 70,60 81,36 >41

SiO2 54,20 62,30 4,95 0,18 0,20 <3

Fe2O3 1,70 1,00 0,75 0,12 0,08 <2

TiO2 1,70 1,40 2,48 -

CaO 0,30 0,10 36,68 27,91 17,00 >49

MgO 0,30 0,30 0,36 0,15 0,14 <2

LOI 7,40 0,31 0,10 1,10 -

Size/mm

G1 %mass 12 24 32 10 2 20

G2 %mass 12 24 32 10 2 20 +3

G3 %mass 12 24 32 10 2 20

G4 %mass 12 24 32 10 2 20

G5 %mass 12 24 32 10 2 20

5/3 3/1 1/0 0,1/0

+0,2 +0,5 +1

100
q = 0,2

10 1 0,1
1 10 100 1000 10000

% base formulation Ideal

microns Graph 1. Particle size distribution of model formulations

Experimental details Figure 1 shows the experimental set up for the gunning tests. An Aliva rotor gun was used with a dry material feed without pre-damping. Water was added via a water mixer body and supplied using a high pressure pump, operating at 8 bar. The water storage tank was coupled to a scale to measure the quantity of water consumed. The gunning nozzle was standard equipment with a 100 cm extension from the water mixer to the nozzle body. The nozzle body was 300 mm long with a taper to an outlet diameter of 35 mm. A pressure gauge monitored the gunning pressure which varied from 2 to 2,5 bar with a gunning hose length of 20 metres.

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% Passing

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3
Pump Material Water Scale

Results

Air inlet

Gunned mass

35 mm 1000 mm 300 mm

Pressure gauge Data logger f(tc) Marine board

Gunning characteristics The amount of dust generated during gunning was very low for all cases and no real distinctions between the various mixes could be seen. In contrast significant differences were observed in terms of gunning behaviour as measured by the water added and the resultant measured rebound. The amount of fine material which dripped from the nozzle (nozzle slop) was also difficult to differentiate between each formulation type and in all cases can be considered as low. The water added at the nozzle was adjusted for each formulation/cement batch and optimised for minimal rebound. The base formulations labelled G1 with Secar 51BTF, Secar 71 and Secar 80 with 2% of clay were not successful. In all cases the adhesion was insufficient and either during the gunning test or immediately after the gunned mass fell to the ground. Therefore the results of these formulations have not been included.

Figure 1. Arrangement of gunning equipment

For each test a total of 250 kg of dry material was gunned on to a vertically suspended board composed of marine plywood; into which 150 mm nails ware placed on 200 mm centres to act as support for the gunned mass. Measured gunning rates ranged from 2 to 3 t/hr. Water adjustment at the nozzle was optimised for each test. After each run the rebound was collected and weighed. The rebound was calculated as a percentage of the total mass gunned with a correction made for water content in the gunned mass and the non adhered material. A thermocouple was inserted into the dry mass to record the exothermic profile. The procedure was based on the same method already published by Lafarge11 over 10 years ago. At the same time the development of hardness was measured using a penetration needle (Maynadier) which gave the resistance to penetration (kg) with the passage of time. After 24 hours the hardened samples were cored and tested for mechanical properties. Parallel tests were conducted on samples of the dry mix cast into samples in the laboratory.

22
Total water demand %

20 18 16 14 12 10 G2 G3 G4

S51BTF S71 S80

G5

Formulation

Graph 2. Total added water

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35 30
Rebound %

Gunned properties The penetration measurements were not possible for the highly accelerated formulation (G3) due to the rapid hardening characteristics. The limit of measurement (40kg) was reached with the first test. This was also the case for the formulations G2 based upon Secar 80. Formulations G3 and G4 for all cement types generally gave similar results. Selective results of the penetration needle tests are presented in Graph 4 for Secar 51BTF and Secar 71. As seen in the graph the addition of the reactive mineral phase (G4) with Secar 51BTF results in a more rapid and greater development of penetration resistance than with the formulation based on a clay addition alone. However the reverse is true for the formulations based upon Secar 71. The rebound values are also shown for each formulation and no apparent correlation is found between the development of penetration resistance and rebound generated.
30,0
Rebound 18,5% Rebound 11,6% Rebound 15,3%

25 20 15 S51BTF 10 5 0 G2 G3 G4 G5 Formulation S71 S80

Graph 3. Total measured rebound

Graphs 2 and 3 show a summary of the results for the other formulations for each cement type tested. Each line represents a cement type. Graph 2 shows the total measured amount of water added expressed as a percentage of the total dry mass gunned (including rebound). With the exception of formulation 2 and Secar 80 the total added water varied from 12% to 14%. The amount of rebound generated (Graph 3) varied according to formulation and cement type with values ranging from 10% to over 25% being recorded. The ability of each formulation to reduce rebound depended upon each cement type. Generally Secar 71 based formulations yielded the lowest rebound figures with values around 10% being recorded. For Secar 51BTF and Secar 71 the formulation G2 based upon a clay addition yielded the lowest figures. With Secar 80 formulations G4 and G5 based upon different additions of the reactive mineral phase yielded lower values but these were higher (20% vs. 10-15%) than the lowest values for Secar 51BTF and Secar 71. The highly accelerated formulations based upon an addition of lithium carbonate showed intermediate behaviour.

20,0
Kg

10,0 0,0 0 20 40

Rebound 16,2%

G2 S51 G4 S51 G2 S71 G4 S71

60 80 100 120 140 Time (mins)

Graph 4. Penetration resistance of gunned samples

The exothermic profiles were recorded for both the gunned samples and laboratory prepared samples. The laboratory samples were maintained with an initial ambient temperature of 20C and enclosed in an insulated cell whereas the field samples were subjected to ambient temperature conditions of 7-12C and no insulation was possible. As a result the field samples reached a maximum temperature of some 10 to 20C lower than the insulated laboratory samples. There was generally good

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agreement between the two methods for the time taken to reach maximum temperature. The results of the field tests are shown in Table 3 with a graphic illustration for the formulations based upon Secar 51BTF in Graph 5.

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Table 3. Exothermic profile data Start of heat generation Mins Secar Secar Secar Secar Secar Secar Secar Secar Secar Secar Secar Secar

Time to max. temp Mins 300 108 258 258 240 75 270 270 168 120 175 185

Max temp C 34,6 36,1 47,5 45,4 44,5 46,1 47,6 45,4 26 31,4 28,5 27

51BTF G2 51BTF G3 51BTF G4 51BTF G5 71 G2 71 G3 71 G4 71 G5 80 G2 80 G3 80 G4 80 G5

140 10 110 110 140 <10 150 150 17 5 17 25

60 50
Temperature

were done on the cored samples both before and after firing. Samples were inspected for signs of defects such as laminations before testing but the cores were found to be homogeneous with very few defects. The mechanical tests as measured by the cold crushing strength are shown in Graphs 6 to 8.
8 10 12 hours
CCS : Mpa

40 30 20 10 0 0 2 G3

G5

G4 G2

80,0 60,0 40,0 20,0 0,0 25h 110C 800C 1100C Treatment temperature C G1 G2 G3 G4

Graph 5. Exothermic profiles for formulations based on Secar 51BTF

As expected the highly accelerated system (G3) shows an almost immediate generation of heat indicating rapid hardening and mechanical strength development due to hydrate formation. This was also evidenced in the laboratory as these formulations could not be placed in moulds before the onset of stiffening. All formulations with Secar 80 showed a more rapid time to maximum heat generation. Mechanical and physical properties After gunning, samples were left for 25 hours before coring and subsequent evaluation of physical as well as mechanical properties. Tests

Graph 6. Cold crushing strength for Secar formulations

51BTF

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80
CCS : Mpa

60 40 20 0 25h 110C 800C 1100C Treatment temperature C

G1 G2 G3 G4

Graph 7. Cold formulations

crushing

strength

for

Secar

71

80,0
CCS : Mpa

The results from the laboratory prepared samples (not shown) had higher values after 25 hours as a result of more ideal curing conditions in the laboratory, otherwise the results were comparable. The density after 110C of both sample types were similar, indicating similar compaction by vibration installation in the laboratory and gunning application in the site tests. Measured densities were all very similar ranging from 2000kg/m3 to 2200 kg/m3 for samples after drying at 110C. After firing at 1100C measured densities ranged from 1900 kg/m3 to 2000-2200 kg/m3. The permanent volume changes were measured from the cored samples to assess whether changing additive type had a significant effect upon volume change. The range measured was from 110C to after firing at 1100C. Previous results8 had suggested that increasing the clay addition was detrimental. The results in Graph 9 show that in all cases a volume shrinkage was recorded but that the increased clay addition (formulations G2) did not necessarily lead to a high volume shrinkage. The highest volume shrinkage was observed for the G3 formulations with lithium carbonate.
Permanent Volume shrinkage %

60,0 40,0 20,0 0,0 25h 110C 800C 1100C Treatment temperature C

G1 G2 G3 G4

Graph 8. Cold formulations

crushing

strength

for

Secar

80

All samples showed the classic changes in mechanical strength that result when conventional castable/gunning systems are fired to 1100C. That is, a decrease in strength during dehydration. In most cases the addition of the reactive mineral phase resulted in improved mechanical performance, although the differences after dehydration i.e. at 800 to 1100C are much less than after drying. The differences were also much less evident with Secar 80 based systems. The differences between the various cement types can be related to the differences in CaO% content in the formulations and the hydraulic potential of each cement type. It is interesting to note that both Secar 71 and Secar 80 show a lower reduction in strength as fired temperature increases than the Secar 51BTF based formulations.

5,0 4,0 3,0 2,0 1,0 0,0 G2 G3 G4 G5 G2 G3 G4 G5 G2 G3 G4 G5 Secar 51BTF Secar 71 Secar 80

Graph 9. Permanent volume change 110C to 1100C

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Discussion
The causes of rebound have been extensively studied within the civil engineering sector13. The key individual factors have been suggested14 to be the added water and gunning technique such as nozzle angle and distance along with material design factors. Particle size distribution, and rheology modifying fine components which act upon the yield stress are shown to be important elements in material design. The mechanism proposed is that impacting particles have an energy of rebound which must be compensated by the adhesion of the particle to the gunned layer to ensure embedment of the particle. The energy was shown to be affected by factors such as water addition and cement content. Thus it is clear from the above models that the additional water will play a key role. An example is shown in Graph 10 for the formulations based on Secar 51BTF where a range of preliminary tests were conducted and the effect of water variation seen.

The installed performance of gunned materials depends to a large degree upon the gunning quality during installation. It has been suggested12 that the gunning quality in turn is affected by both the gunning technique and the material design. Factors such as rebound and adherence (Graphs 2 and 3) can be measured after gunning to asses the overall gunning quality but it is much more difficult to identify and isolate the individual factors within the gunning technique and the material design that contribute to the installed quality. It must also be remembered that optimising an installation parameter such as rebound or adhesion might impact negatively upon the installed mechanical performance. Also the degree of adhesion and rebound are not totally independent. A model has been developed5 which considers the gunned mass to be in a constant state of evolution from a relatively fluid surface to a more viscous plastic phase behind the gunned surface. These layers change as the gunned layer becomes thicker. It is the balance of these layers that determine rebound and adhesion. Too slow, and the evolution into the plastic phase and subsequent stiffening will cause slumping or even falling. For example, the formulations G1 which adhered initially but subsequently fell due to insufficient stiffening within the gunned mass. Too rapid stiffening will increase rebound as the yield stress increases and thus incoming particles would need more kinetic energy to penetrate the gunned surface. This speed of evolution of the rheology phases is linked to material design and the total water added.

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40
CCS 24 hours : Mpa

40

30
Rebound %

30 20 R = 0,333 10
2

20 R = 0,8115 10 0 8 9 10 11 12 13 14 % water added

2

0 9 10 11 12 13 14 % water added

Graph 10. Rebound and C.C.S. as a function of added water for Secar 51BTF formulations

The effect of additional water has a more dramatic effect upon the level of rebound than the mechanical resistance with the range of water tested. The type of additive probably has a more significant effect upon the mechanical strength than the water content within the narrow range tested here. Within the formulations tested two basic types of additives were assessed. The first group are the systems based upon lithium carbonate (formulations G3) which functions as a strong accelerator15. The second system comprising of the clay and the reactive mineral have actions closer to yield stress modification. With these latter systems too high a yield stress will increase rebound as more energy will be required to penetrate the gunned surface. In consequence the particle will have more rebound energy and more adhesion will be required to ensure that it embeds. The penetration tests conducted immediately after gunning with the penetration needle can be considered as a crude measure of the yield stress. Graph 11 shows this relationship for the formulations type G2, G4 and G5.

It is evidenced in this graph that a relationship exists between initial penetration value and the measured rebound. No similar relationship has been found for the highly accelerated systems based on lithium carbonate and no such model exists which can fully explain all the rebound figures shown in Graphs 2 and 3. One of the problems is certainly related to the speed of action with these highly accelerated systems as it is difficult to measure the actual yield stress values at the point of gunning. Afterwards is too late as the stiffening has already occurred and no useful measurements can be made.

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Initial penetration resistance Kg

40 30 R2 = 0,6331 20 10 0 10 15 20 Measured Rebound % 25 30

Graph 11. Measured rebound as a function of initial penetration resistance

The results of the setting time test as measured by the exothermic profiles showed no correlation with the gunning performance with the quickest setting systems not necessarily having the lowest rebound figures. It is clear from the results shown in Graphs 2 to 10 that the interactions between each additive and cement type are not uniform. Therefore no universal solutions exist and optimum solutions must be found for each cement type. For example, from the results presented, Secar 51BTF and Secar 71 can be considered to be the easiest cements to use in gunning applications with good gunning performances along with excellent mechanical strengths being observed. These two cements gave good performance in simple formulations with only a single clay addition. Secar 80 showed the best results when used in combination with clay and the reactive mineral product. This is probably related to the fact that this cement is specifically designed for casting applications while the other products can be considered to be more multi-purpose and therefore easier to apply within gunning applications.

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Conclusions

It appears as if the combination of cement type and additive along with the resultant water addition is critical in determining gunning performance as measured by the material rebound and adherence characteristics. It can be seen from the results presented that conventional gunning formulations can be optimised to yield low rebound products with good installed properties. The exact nature of optimisation will depend upon the calcium aluminate cement type being used. The use of a multiple additive could profitably be employed such as combinations of clay and lithium carbonate to give low rebound whilst assuring excellent adhesion characteristics. The application of Secar 51BTF and Secar 71 in gunning products results in particularly good installation properties whilst maintaining excellent installed properties. Further work will concentrate on identifying the individual levers responsible for gunning behaviour as well as investigating the effect of reducing the cement content formulations.

10

11

Acknowledgments

12 13 14

The authors would like to thank all the co workers at who contributed to the studies that led to this paper.

7
1

References

15

Bier Th; Bunt N.E; Parr C; Calcium Aluminate bonded castables their advantages and applications; Alafar proceedings; 1996.

Valdelivre B, Parr C, Bier Th; Medium cement castables; Alafar proceedings ; 1997. Bier Th, Mathieu A, Parr C; "Calcium Aluminates in self flowing castables"; Silicate Society conference; Prague 1996. Mathieu A; "Calcium Aluminates in self flowing castables"; Brazilian Ceramic association Aguas de Lindoia; Brazil ; June 1995. Landman et al; The rehabilitation of gunning refractories; 2nd. International conference on refractories; Japan; 1987. Biever et al; The characterisation of reduced cement, high strength abrasion resistant gunning castable refractories; Anaheim; Unitecr 1989. Tabata et al; Application of high density gunning mix for repair of Torpedo Ladle; p110-p113 Aachen conference proceedings 1988. Fisher R.E.; Critical issues for successful performance; St. Louis section meeting; American ceramic society, 1996. W.G. Allen; "Advanced equipment systems for refractory placement"; UNITECR proceedings 1997. Dinger D and Funk J; Predictive process control of crowded particulate suspensions Kluwer academic publishers; USA; 1994. Fentiman G; Montgomery R; The heat evolution test for setting time of cements and castables; Advances in ceramics; 13 ; 1985 Franz Petio ; Top quality gunning mixes for BOF; UNITECR proceedings 1997. Armelin et al; Rebound in Dry-Mix Shotcrete; Concrete international; September 1997 p54-p60. Armelin et al; Mechanics of aggregate rebound in Shotcrete (Part 1); Materials and Structures; Vol. 31, March 1998; p91-p98. Th. A. Bier; "Admixtures and their interactions with high range calcium aluminate cement"; UNITECR 1995.

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