CALCIUM ALUMINATE CEMENTS

Submitted By:

Jatinderjit Singh
(07D04020)

Under the guidance of

Prof. Prakash Nanthagopalan

Department Of Civil Engineering Indian Institute of Technology Bombay

Contents
1. Introduction ........................................................................................................................................ 1 2. Manufacture ....................................................................................................................................... 1 3. Hydration and Conversion .................................................................................................................. 2 4. Properties of fresh CAC concrete ........................................................................................................ 4 4.1 Setting ........................................................................................................................................... 4 4.2 Workability .................................................................................................................................... 5 4.3 Rate of reaction and heat evolution ............................................................................................. 5 4.4 Shrinkage....................................................................................................................................... 6 5. Properties and Applications ................................................................................................................ 6 5.1 Performance at high temperatures .............................................................................................. 6 5.2 Resistance to acid attack............................................................................................................... 7 5.3 Resistance to abrasion .................................................................................................................. 8 5.4 Thermal resistance ........................................................................................................................ 9 5.5 Other applications......................................................................................................................... 9 6. Structural collapses associated with CAC concrete .......................................................................... 10 7. Conclusion ......................................................................................................................................... 10 References 11

1. Introduction
Calcium aluminate cements (CACs) are the most important type of non-Portland or special cements. Even so, the volume used each year is only about one thousandth of that of Portland cement. As they are considerably more expensive (four to five times), it is therefore not economic to use them as a simple substitute for Portland cement. They do not compete with the latter in any application where concrete made with Portland cement performs satisfactorily. However, there are applications in which the unique properties of calcium aluminate cements enable them to be used in severe environments where they are often in competition with non-cementitious materials.

Fig. 2 Composition range of Calcium Aluminate Cements

CACs are produced with a wide range of alumina (Al2O3) contents from around 4080%. The higher alumina content grades are made from relatively pure raw materials (metallurgical alumina and lime), which make them very expensive. A few distinct advantages CAC concrete has over traditional Portland cement concrete: rapid strength gain upon setting enhanced resistance to abrasion, sulphate attack and alkalisilica reaction production of CAC results in lower CO2 emissions than Portland cement production

2. Manufacture
The most common method of manufacturing today is using the open-hearth furnace. is arranged with a long vertical stack into which the bauxite and limestone, or chalk are charged. It is fired with pulverised coal or oil with a hot-air blast. The furnace gases pass through the charge of the raw materials, driving off water and carbon dioxide. Melting occurs at the point where the charge drops from the vertical stack into the hearth of the furnace. Because complete melting usually takes place, raw materials in lump-form can be used. The cement is maintained in a liquid state in the hearth by heat radiated from the arched roof. The molten cement pours out continuously from a tap hole, and is run into moulds and cooled. The temperature reached is above 1450C. Electric furnaces are also used in some plants. These furnaces are tapped intermittently and so have a fairly low output. After cooling, the fused cement clinker resembles a dark, fine-grained compact rock such as basalt. The clinker ingots are crushed and then ground in ball mills. The cement is very hard to grind, 1

resulting in high power consumption and heavy wear on the grinding equipment. In contrast to Portland cements, where gypsum is added to regulate setting, no additions are made during grinding, the setting time being controlled primarily by the composition. Grades of higher aluminate content (60-80 per cent Al2O3) are usually made by sintering in rotary kilns. As alumina is used instead of bauxite, they contain practically no silica or iron oxide and are white in colour. These grades are predominantly used as binding agents in castable refractories, although they are also used in some building chemistry formulations.

Fig. 2 Reverberatory Furnace

3. Hydration and Conversion

Portland cements contain lime (CaO) and silica (SiO2) as the principal oxides, in the form of tricalcium and dicalcium silicate (C3S and C2S). On reaction with water, amorphous calcium silicate hydrate (C-SH) and crystalline calcium hydroxide (CH) are the principal hydrates formed. In contrast, CACs contain CaO and Al2O3 as the principal oxides, with little or no silica. These combine to give monocalciumaluminate (CA) as the principal active phase in the cement, which reacts with water to give calcium aluminate hydrates. Sometimes it is quite difficult for the stable phases to form immediately due to the rearrangement of ions that needs to occur (nucleation). In this case it often happens that different phases form temporarily, which are metastable. They have a lower energy than the starting phase assemblage, which provides a driving force for their formation, but they have a higher energy than the stable phase assemblage. Thus a driving force remains for the meta-stable phases to in turn react to give the stable phase assemblage. 2

On reaction with water the nature of the hydrates formed is dependent on the temperature of hydration, as shown in Fig. 3. At lower temperatures CAH10 is the first hydrate formed, at intermediate temperatures C2AH8 and AH3, and at higher temperatures C3AH6 and AH3. The stable phases are C3AH6 and AH3, and the other phases will inevitably convert to these at a rate dependent on temperature and moisture. C3AH6 has the highest density of the calcium aluminate hydrates, resulting in a higher porosity at a given degree of hydration. However, the conversion reaction also leads to the release of water, which is available for further reaction of remaining anhydrous material. For this reason the strength development curve of calcium aluminate cement concretes, in small sections at ambient temperatures, has the form shown in Fig. 2, with an initial rapid increase to a high early strength (corresponding to CAH10 and C2AH8) followed by a slow decline to a minimum (during the transformation to C3AH6 and AH3) before a further increase.

Fig. 3 Hydration Reactions of monocalcium aluminate

Fig. 4 Schematic strength development of calcium aluminate at a water cement ration of about 0.4

Control of the initial water-to-cement (w/c) ratio is very important to ensure that the minimum strength is sufficient for the application and design must always be on the basis of this long-term strength. Over 60 years of practical and laboratory experience has shown that good long-term durability requires a w/c ratio at or below 0.4, and that in the absence of superplasticizers this necessitates a cement content of more than 400 kg/m3.

Due to the rapid hydration reaction, there is a large release of heat during the early stages of hydration. The consequences of this release are that sections of more than a few tens of centimetres in thickness will attain temperature of up to 70C or more during curing. Thus the conversion reaction will occur almost instantaneously, leading to a continuously increasing development of strength. Properties of hydrates:

Fig. 5 Key Properties and Micrographs of the calcium aluminium hydrates

4. Properties of fresh CAC concrete

4.1 Setting
The setting times of calcium aluminate cements are similar to those of Portland cement, namely around 35 hours. The setting time of calcium aluminate phases becomes progressively longer with decreasing lime-to-alumina ratio. C3A, the lime rich phase present in Portland cements, reacts rapidly with water, necessitating the addition of gypsum to Portland cement clinker to prevent flash

setting. At the other extreme CA2 reacts extremely slowly and CA6 is inert at ambient temperatures. The setting time of pure CA is typically about 18 hours, but the shorter setting time seen in calcium aluminate cements is due to the disproportionate effect of the small quantities of lime-rich C12A7 phase present. Because of this strong effect of C12A7, variations in its amount can cause the setting time to change by hours and excessive amounts can cause early stiffening. The amount of C12A7 is therefore tightly controlled during production to avoid this variability in setting time and other properties that may also be affected as a consequence.

4.2 Workability
In the absence of admixtures the intrinsic ease of placing CAC concretes is similar to that of Portland concretes at the same water-to-cement ratio. CAC concretes appear dryer, but they flow well under vibration. It is important to have a well-graded aggregate, particularly sufficient fine sand, to minimize the volume between the aggregates that the cement paste needs to fill. Classic plasticizers such as ligno-sulphonate and sodium citrate work reasonably well with CACs, but there may be a significant retarding effect. Superplasticizers based on naphthalene and melamine sulphonate are not very effective. Until recently, the best way of obtaining reasonable workability at the recommended low w/c ratios was to use high cement content, typically more than 400 kg/m3.

4.3 Rate of reaction and heat evolution

In Portland cement the main hydration product is deposited around the hydrating cement grains, so that after the first few hours the rate of reaction is progressively slowed down. In CACs, in contrast, the hydration products are deposited throughout space. The rate of reaction only slows due to one of the reactants (water or cement) being used up or to lack of space for the hydrates to precipitate. This pattern of reaction leads to the rapid hardening of CAC concrete and it is quite easy to obtain strengths of more than 20 MPa at 6 hours and over 40 MPa at 24 hours.

Fig. 6 - Schematic representation of the deposition of hydration products for the hydration of Portland and calcium aluminate cement

The other consequence of the rapid reaction is that the heat of hydration is evolved over a relatively short time. As the heat generation is rapid relative to the rate of heat dissipation, self-heating may be considerable in sections more than about 100 mm in size. It is quite usual to have maximum temperature in the range 5080C or even higher.

Fig. 7 - Temperature rise in beam 35x180cm of CAC concrete. Formwork was removed after 5 hrs then sprayed with water for 20 hours. Adapted from French Standard (1991)

4.4 Shrinkage
Intrinsically the shrinkage of calcium aluminate cement is roughly similar to that of Portland cement at the same degree of hydration. However, as hydration occurs much more rapidly this shrinkage occurs over much shorter period of time and can lead to problems with early age cracking

Fig. 8 - Comparision of shrinkage for CAC and OPC concrete measured in 40x40x160 prisms at 20C, 50% RH. Data from French Standard (1991)

In order to minimize these effects the same rules of concrete technology that are known for Portland cements apply, namely: prolonged moist curing good aggregate grading to minimize paste volume limitation of bay sizes (to around 3 m in unreinforced slabs) use of polymeric fibres in thin sections.

5. Properties and Applications

5.1 Performance at high temperatures
OPC has limited use at high temperatures for a number of reasons. At temperatures of ~500C the hydrated lime or Portlandite (Ca(OH)2), which forms a significant proportion of hydrated Portland cement, will dehydrate to form quicklime (CaO). This is a reversible reaction: ()2 + 2

Exposure to moisture (atmospheric moisture is sufficient) leads to rehydration of the quicklime which is an expansive reaction and will disrupt the concrete. Thus any application where there is cycling between high temperatures and ambient temperatures is excluded. Furthermore, Portland cement is high in lime and silica, which form low melting point compounds at the service temperature of the refractory concretes.

Fig. 9 Portland cement and calcium aluminate cement concrete cylinders after 8 cycles of 6 hours at 500C, followed by 24 hours in humid conditions

Hydrated lime is not formed during the hydration of CAC. Thus it is not subject to the disruption caused by the rehydration of quicklime. The hydrates that are formed do dehydrate progressively as the temperature increases to about 300C and above. However, the compounds formed are themselves stable and at even higher temperatures (>1000C) begin to react with the refractory aggregates to form new stable phases.

5.2 Resistance to acid attack

Alumina hydrate is stable down to a pH of about 3 or 4 and the dissolution of the calcium component of the other hydrates leads to the formation of additional quantities of this phase, which infills pores, protecting the concrete from further attack and generally giving a smoother attacked surface with less aggregate loss. 3 6 + 6 + 32+ + 2()3 +62 Below a pH of around 3.5 the alumina hydrate dissolves, but in so doing neutralises more acid: 3 + 6 + 2 3+ + 62 Overall, the neutralisation reaction is: 3 6 + 23 + 24 + 32+ + 6 + + 242 Due to better performance of CAC concrete against acids, it finds applications in sewage pipes.

Fig. 10 - Sewage pipes after 12 years in a field trial in South Africa. The Portland/siliceous aggregate section (a) has completely eroded through its 60 mm thickness in places. The CAC/siliceous aggregate section (b) shows maximum erosion of 1015 mm only at the water-line.

5.3 Resistance to abrasion

The observed good performance of CAC concretes in environments subject to abrasion has led to it being used increasingly for repairs to hydraulic dams in areas susceptible to abrasion (spillways, sluice gates, and flushing tunnel linings). CAC concrete with synthetic aggregate perform significantly better than Portland cement concretes (even high-performance concretes with silica fume) and similar to or better than granite blocks, which have been widely used in such application. Recent tests in India on the abrasion of concretes under practical conditions of rapid evacuation (fast flowing water, 50 m/s, charged by fine silt) showed a degradation of 3050 mm of high-performance Portland/silica fume concrete with steel fibres, compared to 25 mm of CAC/synthetic aggregate concrete. The higher materials cost of calcium aluminate cements translates into an installed cost about two and a half times greater than conventional concretes, but only half that of the installed cost of granite blocks and considerably less than steel or cast iron plates, which are often used in areas that suffer from severe abrasion. Thus the calcium aluminate cement concrete provides a viable solution on a cost-performance basis.

Fig. 11 Dam flushing gate, abrasion resistance

5.4 Thermal resistance

CAC concrete is very resistant to heating and thermal shock. This property, along with aspect of resistance to abrasion to abrasion, advocates its use in foundry floors. Another use drawing on this property is in buildings for fire training, which can withstand repeated lighting and extinguishing of fires.

Fig. 12 Foundry floor, abrasion and thermal shock resistance

Fig. 13 Cryogenic facility, thermal shock, freeze-thaw

5.5 Other applications

Construction concretes, rapid strength development is achieved, even at low temperatures.

Fig. 14 Bridge widening, rapid hardening

6. Structural collapses associated with CAC concrete

There were a few structural collapses in Europe during the third quarter of the 20th century. The origin of these was the use of CAC concrete. At the time, conversion was known about, but the advice was conflicting. Rather than conversion being regarded as inevitable, it was considered to be negligibly slow if warm moist environments were avoided. Nevertheless, loss of strength due to conversion was not the sole or primary cause of failure. In two out of the three incidents design problems were the primary cause. In another case, the concrete was found to have degraded due to external sulphate attack from adjacent plaster. This attack was facilitated by the high porosity of the concrete due to the use of a high w/c. The overall number of buildings containing CAC concrete built during this period which continue in service is believed to be around 30 00050 000. After the collapses some 1022 of these were inspected, of which 38 were identified as having problems, but in only one of these was this attributed to loss of strength due to conversion.

7. Conclusion
Due to conversion, which leads to an increase in porosity and subsequent decrease in strength, there has been a shift away from the usage of CAC. Several building collapses in the 1970s were initially (wrongly) attributed to CAC conversion, and many structural codes subsequently banned use of the material. Since this time, intensive research has provided a greater understanding of CAC chemistry and behaviour. A report by the Concrete Society in 1997 provided improved guidance for predicting long-term properties, and, as a result, the technical concrete market has seen resurgence in interest and use of this alternative cementitious binder. The few examples given here illustrate how specific environmental conditions can justify the use of a higher cost raw material to gain better life cycle cost and fulfil niches in which Portland cement does not perform satisfactorily. But CAC is way too expensive compared to Portland cement, with the cost related directly to the limited supply of bauxite, the main source of alumina in CAC production. Its cost is about 5-6 times more than Portland cement. Due to this CAC cannot be used as a primary binder, and cannot replace OPC for normal construction as freely. So it is currently suitable for specific conditions only.

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References
[1] Karen L. Scrivener, Jean-Louis Cabiron, Roger Letourneux, High-performance concretes from calcium aluminate cements, Cement and Concrete Research 29 (1999) 12151223 [2] Karen L. Scrivener, in:John Newman, Ban Seng Choo, Advanced Concrete Technology- Constituent Materials, 2003 [3] K.L. Scrivener, Calcium aluminate cements, in: P.C. Hewlett (Ed.), LEAS Chemistry of Cement and Concrete, 4th ed., 1998 [4] Chris Parr, Calcium Aluminate Cements What Happens When Things Go Wrong, IRE annual conference, Rotham UK, September 2008 [5] Wikipedia - http://en.wikipedia.org/wiki/Calcium_aluminate_cements [6] Technology of Calcium Aluminates - http://www.kerneos.com/-Technology-of-calciumaluminates-

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