4.

0 Discussion of anhydrous cement preparation

The production of ordinary Portland and calcium sulpho-aluminate cement by rotary calcining kilns, as discussed in the introduction, is based on huge volumes measured in tonnes of clinker per hour. Changing the composition of the cement or raw meal during production may not only cause undesirable variation in the performance of the cement, but can strip the lining out of a cement kiln. These are just two of the many reasons cement manufacturers go to extreme lengths to maintain the continuity of their production1.

To investigate the production of ettringite it was necessary to test the effects of changes in the cement composition. To do this small laboratory samples of cement with various compositions had to be prepared under repeatable and controlled conditions.

4.1 Modification of the Bogue equation

The Bogue equation, as introduced in the introduction, cannot be applied to the formation of calcium sulpho-aluminate cement. To be able to generate the different calcium sulpho-aluminate type cements required, a modification of the Bogue equation needed to be produced. A number of different trial cements were produced to ascertain the sequence of crystal formation when cements are formed (Method 2.27 Results 3.6.1).

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A number of different cements were then prepared with excess levels of each oxide. The mineral content of each was examined by XRPD to ascertain the form the excess component occurred in (Results 3.6). The summation of this information allowed the empirical equation (Figure 4.1) to be devised.

Figure 4.1 Bogue type equation for CSA

w/w % C2S C4AF C4A3 = = = 2.86 x SiO2 3.0375 x Fe2O3 7.625 x SO3 - 1.2708 x Fe2O3 1.9412 x Al2O3 - 2.33 x SO3 - 1.2375 x Fe2O3

C12A7 =

FREE LIME = CaO - O.65 x C2S - 0.461 x C4AF-0.367 x C4A3

- 0.485 x C12A7

Assumption Assumption

:- Free lime >= 0 :- The elements are fully dispersed through the system during calcination.

The basic premise for the above equation was that phases crystallise sequentially from the general mass as it cools. The equation does not take into account the possibility of solid solutions between the different phases. Crystallographic examination of the test cements prepared (Results 3.1) showed there to be no deviation in the observed patterns from the data standards, suggesting that there is no solid solution between C2S , 118

C4AF, C4A3

and C12A7 . The phases are listed in descending order of

crystallisation temperature. Values for the oxides used in the equation are the mass percentage as determined by XRF. The resultant mineral prediction is as mass percentage composition.

The equation was tested several times by making the cement and empirically matching the result to the predicted composition (Method 2.27). The equation was then used to manufacture a specifically prepared cement for the production of ettringite (Method 2.27 Results 3.6.1).

4.2.1 Preparation of cement samples in a muffle furnace.

Gartner5, Gies7 and Suzuki28 describe methods for preparing cement samples using crucibles and muffle furnaces (Method 2.9). Most literature methods refer to small pressed pellets of the cement raw materials in the correct stoichiometric ratio. The crucible was then placed in a muffle furnace at various temperatures ranging from 1125-1500 oC for 30-240 minutes.

To examine the effect of the crucible on the phases formed, the correct stochiometric amounts of the raw materials were placed in silicon, mullite and alumina crucibles (Method 2.9). The crucibles were then heated in a muffle furnace. The temperature used depended on the literature values for the phases being prepared. No changes were observed in the crucible and it was assumed that the crucible material had no effect on the cement raw materials.

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4.2.2 Preparation of a pure sample of CSA clinker using a Muffle furnace

An attempt to produce a pure sample of calcium sulpho-aluminate cement by literature29 methods was made (Method 2.10), using a muffle furnace. The resultant clinker was loosely bound and contained a large quantity of unsintered powder. A sample was examined by x-ray powder diffraction and found to contain mainly calcium oxide, aluminium oxide and a small amount of calcium aluminate. It was found that almost all the sulphates had been lost during the preparation. A second problem with the method used was the small size of the cement sample being produced. The investigation required cement sample sizes in excess of 2000 g to be prepared. The method was deemed unacceptable to produce samples of Kleins compound for the investigation.

4.3.1 Preparation of cement samples in an Inductotherm coreless induction furnace

D.Menetrier-Sorrentino, C.M.George & F.P.Sorrentino30 describe

using a

fusion technique to produce alumina cements of varying phases. To reach the high temperatures required by fusion techniques, a metallurgical furnace was employed (Method 2.11). The smallest furnace available would normally be capable of melting 10 kg of steel. This allowed about 3000 g of cement

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raw materials in the correct stochiometric ratio to be used in this technique. The powders were dampened and compressed into blocks. The blocks were then placed in an Inductotherm coreless induction furnace. The furnace functions by inducing a high frequency current in the sample to be melted. As the raw materials did not conduct electricity a graphite crucible was used. The crucible was heated by induction and the sample heated by the crucible.

The fine control of the furnace proved difficult even with the help of the experienced operator. The samples rapidly heated and melted at about 1500oC. Temperature measurement of the contents was impossible using thermocouples while the furnace was running due to induced current in the thermocouple. When the induction current was turned off it was found that the induction coil cooling system rapidly cooled the crucible and a stable temperature was impossible. An optical pyrometer was tested, however the reading was dependant on the temperature of the cooler surface of the cement. The pyrometer was found to be less accurate than the thermocouple.

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4.3.2 Production of mixed phase alumina cement in an induction furnace.

A number of alumina cements were prepared using the induction furnace to identify the sequence of mineral formation during cooling from a general melt. The mineral content and the activity of the cements were compared to known commercial cements. Sufficient materials to give 2000 g of each cement were prepared by blending calcium carbonate, aluminium oxide and iron oxide in the correct stochiometric ratio. The blend was dampened and compressed into blocks. These were then placed in the furnace and heated until fully molten. The molten liquid was then poured out into copper moulds to allow fairly rapid cooling Fig 4.2

Figure 4.2 Pouring of molten HAC into copper moulds

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The cooled clinker formed was then broken up and ground in a ball mill until the required surface area was achieved (Method 2.12). The surface area of the cements was determined using a calibrated R and B instruments specific surface area machine. The phases present in the clinker were identified by Xray powder diffraction. The oxide composition of the clinker was determined by X-ray efflorescence (Method 2.24,Results 3.10). The method was then tested by preparing calcium silicates. The high rate of cooling via quenching9 by poring the melt into cold copper moulds allowed the formation of -C2S. The -C2S subsequently converted back to -C2S on exposure to the atmosphere.

4.3.3 Preparation of a pure sample of CSA clinker using an induction furnace

An attempt was made to prepare Kliens compound (yeelimite) in the induction furnace as detailed above. The clinker produced was examined by xray powder diffraction and found to contain mainly the minerals mayenite and mono -calcium aluminate. The hot graphite caused highly reducing

conditions to exist within the crucible and as a result almost all of the sulphur was lost to the atmosphere as sulphur dioxide. Although unsuitable for the production of calcium sulpho-aluminate the method was deemed to be acceptable for the production of alumina and calcium silicate cements.

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4.4 Construction of a bench scale rotary cement kiln

It was decided that the Methods 2.9 and 2.11 were unsuitable for the production of calcium sulpho-aluminate cement. A purpose designed and constructed furnace was prepared specifically to replicate conditions within rotary cement kilns.

The furnace was constructed by adapting a Carbolite 960 mm long 1500 oC, 50 mm diameter, tube furnace. The furnace was fitted with a 1200 mm Mullite worktube. The ends of the worktube protruded out either end of the furnace. A finely controlled rotary drive mechanism was fitted to the extended worktube. The insulation was cut away so that the work tube rotated freely. An integrated 9000 series single zone temperature controller was fitted to allow good temperature control to be exercised. Figures 4.3 and 4.4 are diagrammatic representations of the furnace showing the various features of the furnace. A photograph (Figure 4.5) shows the final working version.

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Figure 4.3
D ia g r a m a t ic a l r e p r e s e n t a t io n o f th e b e n c h s c a le f u r n a c e

Worktube

Drive mechanism
1435

Temperature controller

Drive control

Figure 4.4
Bench scale rotary kiln (internal arrangement) Silicon carbide elements Raw Meal

Re-crystallised Alumina work tube

Insulation

Quench zone

Calcining region

Pre heat zone Variable inclination

Clinker Power light Load switch Load light Temperature controller Variable speed drive controller
1435

Variable speed drive

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Figure 4.5 Photograph of the working furnace.

4.4.1 Initial clinker production

The elemental content of an existing Chinese calcium sulpho-aluminate cement was obtained by XRF (Results 3.10). A sample raw meal with the same elemental analysis was prepared using Chinese bauxite, limestone, silica fume and anhydrite. The ground powders were then suspended as a slurry in water. The slurry was then heated to drive off most of the water. The sticky paste was rolled into balls ready to be placed in the furnace. The furnace was heated to 1200oC, the literature value for the formation of calcium sulphoaluminate clinker2,3,4. The balls were introduced into the pre-heater zone of the furnace. The residence time in the hot zone was limited to 30 minutes.

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The progression of the reaction mixture was controlled by the inclination angle and speed of rotation of the work tube.

The clinker produced was examined for texture. The free lime content was crudely determined by measuring the temperature rise by thermocouple, of a crushed clinker /water mixture. The clinker was found to show a reasonable level of exothermic behaviour. The temperature of the furnace was increased in two 50 oC increments until the clinker showed no exothermic behaviour.

The furnace temperature was then raised slowly in 3-4 oC increments until the clinker became slightly tacky, partially adhering to the worktube walls. At a temperature of 1338oC the clinker on a macroscopic scale closely resembled the sample produced in China. The experimental clinker was ground and examined by XRD and XRF to determine any changes that had occurred. The results (Results 3.6.1) obtained indicated that clinker formation had been successful.

4.4.2 Production of pure samples of C4A3

Analar calcium carbonate, calcium sulphate and aluminium hydroxide in the correct stochiometric ratio were blended as a slurry in water. These were then dried to a stiff gel in an oven. The furnace was heated to 1345oC. The raw meal was lightly crushed to form angular chunks. The raw meal was then added to the preheater zone of the worktube and allowed to pass through the

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furnace, residing in the hot zone for 30 minutes. The very pale sky blue clinker was obtained. The clinker was examined by XRD to determine the mineralogical composition. The composition of the clinker was determined to be exclusively yeelimite(results 3.6.1). XRF and gravametric analysis indicated that very little SO3 had been lost during calcination.

4.4.3 Observation of clinker formation

As the bench scale furnace was run it was noticed that several different artefacts could be observed forming in the work tube. Five separate zones could be observed. A thermocouple was introduced into the furnace to ascertain the temperature at which these artefacts occurred.

Figure4.6 Cross section through the furnace work tube

Worktube

Cement particle deposits

zone 5

zone 4

zone 3

zone 2

zone 1

1345

1143 o Temperature in C

100

20

The different zones were examined and samples of clinker from the different regions were obtained for XRF and XRD examination. 128

Zone 1:

The zone had little or no deposits of raw meal. However, it was

a condensation zone for the water used as a binder and a flux. The raw meal was very wet at the extreme right hand (cold) side and quite dry at the (hot) left hand side. Zone 2: A soft loosely bound ring rapidly formed in this region. There

were no obvious chemical changes occurring in the raw meal. It is suggested that this was the point at which the water of crystallisation of the gypsum lost in zone 3 was absorbed by the incoming dried raw meal. Zone 3: Considerable chemical changes were observed in this region.

Gypsum was converted to anhydrite and calcium carbonate was converted to calcium oxide. Zone 4: A second ring was observed to form in this region. On analysis

(Method 2.24,Results 3.10) it was found that the ring material contained a disproportionate amount of sulphur when compared to the raw meal sulphur content. Zone 5: This zone contained clinker. The deposits on the surface of the

worktube were found to be indistinguishable from the clinker composition.

4.5 Effect of doping on the stability of calcium silicate

When very high calcium silicate cements were prepared a sixth zone was observed. The zone occurred at the cooling end of the furnace where the conversion of beta dicalcium silicate to the gamma form occurred. The temperature of this conversion was investigated and found to be 530 oC. Pure

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samples of dicalcium silicate were then prepared and placed in the furnace. The temperature of the visual conversion was measured by thermocouple, and found to be 823 oC

Samples of different bauxite were used to prepare a range of standard calcium sulpho-aluminate compositions as predicted by the computer composition model (Appendix 4). The cement was prepared using unusually high levels of silica, when compared to Chinease CSA, within the system. It was proposed to test the suggestion that high levels of sulphur present preferentially direct,away from formation of C3S to the formation C2S. A second phenomenon visually observed, was the secondary conversion of C2S to -C2S. It was found that only the calcium sulpho-aluminate produced from Chinese bauxite gave an apparently stable clinker.

Close examination of the Chinese bauxite composition by XRF indicated that the bauxite was heavily contaminated with a range of different elements(Results 3.10).

It is suggested that high levels of sulphur preferentially directs the formation of C2S as opposed to C3S. This effect is observed even in systems where there is an excess of calcium and aluminium. It is further indicated that the presence of the contaminant oxides help to stabilise higher energy polymorphs of C2S.

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It was decided to try three different clinkers to separate the two effects observed above. A test was performed where a sample of C2S was prepared ( Method 2.27) from GPR silica, CaCO3 and anhydrite. A second test was prepared ( Method 2.27) using only GPR silica, CaCO3. The third test used stoichiometricaly correct amounts of calcium oxide and silica for C2S, however there was a 0.5% w/w vanadium pentoxide inclusion to act as a phase stabiliser ( Method 2.27). The clinkers were calcined at 1593oC (maximum temp obtainable in the furnace) and the stability noted.

The resultant clinker from the first test was sea green in colour and stable. XRD examinations suggested (Results 3.6.1) that the clinker was calcium silicate sulphate (Ca5(SiO4)2SO4) and excess anhydrite. This cement was unreactive to hydration. The second clinker remained white, however, it showed expansive disruption on cooling, occurring at approximately 800oC. XRD examinations showed there to be both C3S and -C2S present (Results 3.6.1). The composition suggested that all the calcium was consumed. The third clinker was white and showed some expansive disruption. On XRD examination the clinker was shown to be a mixture of CaO, -C2S and -C2S (Results 3.6.1). A sample of bauxite was obtained from Madagascar via Ireland. This was used to produce a calcium sulpho-aluminate similar to the Chinese calcium sulphoaluminate. Interestingly; the clinker disruptively expanded with the conversion of -C2S to -C2S. The process was photographed (Figure 4.7) to show the speed and degree of disruption.

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Figure 4.7 Clinker undergoing disruptive expansion.

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4.6 Preparation of an ideal cement for the production of ettringite

The mechanism proposed in the discussion section 5.3, was used to design a high reactivity cement. Ideally the cement would have a number of specific characteristics.

1. The cement should have a high alumina content. 2. The cement should be friable. 3. The cement should contain calcium, aluminium and sulphate in the clinker. 4. The cement should be exothermic when mixed with water. 5. The cement should be capable of forming seed sites. 6. The cement should contain a high energy calcium silicate polymorph. 7. The cement should be capable of being formed at relatively low temperatures 8. The inclusion of a slowly hydrating aluminate phase to allow continuous ettringite formation would be advantageous.

It was decided that mayenite, would be a fair candidate for the aluminate phase. However, mayenite is not friable nor does it contain all the target elements for the formationn of ettringite. It was decided to dope the mayenite with a small amount of yeelimite C4A3 . A sample was prepared and

calcined at 1404 oC (Method 2.27). The clinker produced was soft and easily ground. It was found that the cement set within 5 mins without accelerators
26,30

. On addition of lithium carbonate the cement set and exothermed

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sufficiently to melt a polystyrene cup within 3 mins at 0.5 w:p ratio. Hydrated cement samples were left in the lab for 7 days. The hardened pastes showed expansive cracking. The cement was tested in a simple grout (Method 2.4) to estimate the cements ability to form ettringite.

The cement appeared to fulfil all the requirements 1-5 & 7, however , the cement failed to fulfil item 6. An attempt (Method 2.27) was made to produce a high silica version. Unfortunately; the cement did not form dicalcium silicate but tricalcium silicate with some free alumina. It was decided that the sulphate level was too low to direct the silicon to form dicalcium silicate.

A second attempt, (Method 2.27) combined high silicon, sulphate, calcium, and aluminium in the preferred ratio to generate grout 2120. The clinker generated was extremely hard and ceramic in nature. The hardness of the clinker was such that it was quite resistant to grinding. This route was abandoned.

It was concluded that the original Chinese calcium sulpho-aluminate cement was extremely close to the required target cement. Any increase in the belite content resulted in expansive disruption due to -C2S to -C2S conversion occuring on cooling.

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