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INTERNATIONAL CONFERENCE ON SUSTAINABILITY IN THE CEMENT AND CONCRETE

INDUSTRY – Lillehammer, Norway, 16 – 19 September 2007

Low-CO2 Cements based on Calcium Sulfoaluminates

by Ellis Gartner, Lafarge Central Research, France and Keith Quillin, BRE, Garston, Watford,
UK

SUMMARY

The production of clinkers rich in calcium sulfoaluminate (CSA) requires less limestone and
less energy than the production of conventional Portland cement clinkers. Consequently, CO2
emissions per unit of clinker are reduced. Experimental results also show that CSA-based
cements can be formulated to produce durable concretes with physical properties comparable
to those of common classes of Portland cement concrete. Overall CO2 emissions with such
cements can be significantly lower than with conventional cements based on Portland clinker.
Two main avenues of research were followed with a view to balancing environmental impact,
manufacturing costs and physical performance:
1. Blends of calcium-sulfoaluminate-rich cements with non-clinker materials such as
ground granulated blastfurnace slag (ggbs) and calcium sulfate. Certain blended
cements of this type were found to give concretes with good physical properties. They
were demonstrated to be suitable for the manufacture of precast concrete blocks.

2. Cements based on novel clinkers containing activated belite, calcium sulfoaluminate


and calcium aluminoferrite. Such clinkers can potentially be manufactured from a
wide range of raw materials, emitting 20-25% less CO2 than Portland cement clinker.
Concrete compressive strength development to 90 days was shown to be comparable
with an otherwise equivalent concrete made using a conventional OPC (42.5R).

However, developing new cements like these for large scale use is an inherently slow process,
and a great deal more work is still required to:
• Confirm that such cements can be manufactured industrially, with the desired CO2
emissions savings and low environmental impact, and at an acceptable cost.
• Better establish the effects of compositional and processing variables on performance.
• Optimise cements for performance in various major use categories, in terms of
physical properties, raw materials availability, manufacturing parameters, etc.
• Develop the scientific understanding necessary to explain the observed performance,
and thus to help predict the effect of variations in conditions on such performance.
• Clearly establish the long term performance of these materials in concrete and provide
data that will give users and specifiers confidence in their durability.
• Develop appropriate codes and standards for their use in construction.

INTRODUCTION

Global cement manufacture (including both “pure” and “blended” Portland cements) has risen
from 594 million tonnes per annum in 1970 to 2284 million tonnes per annum in 2005 with
virtually all of this growth occurring in developing countries. Global production is likely to
increase significantly over the coming decades as the global population increases. Recent
INTERNATIONAL CONFERENCE ON SUSTAINABILITY IN THE CEMENT AND CONCRETE
INDUSTRY – Lillehammer, Norway, 16 – 19 September 2007

forecasts have suggested that global cement production could exceed 5 billion tonnes per
annum by 2050.

Cement manufacture is energy intensive. The raw materials must be finely ground and
homogenised, and then heated to about 1450oC to form “Portland cement clinker”. Upon
cooling, the hard nodules of clinker must then be finely ground, with small amounts of other
ingredients such as gypsum, to make the finished cement . Energy consumption as fuel and
electricity consequently represents about 65-70% of the variable costs associated with
Portland cement manufacture1,2.

Cement manufacture also produces large amounts of CO2 due directly to the calcination of
CaCO3 (about 1.2 tonnes of limestone are required to produce one tonne of a typical modern
Portland cement clinker). The amount of CO2 emitted per unit of Portland cement clinker
manufactured depends on a number of factors such as clinker type, fuel and raw materials
compositions and the energy efficiency of the specific kiln system. The amount of CO2
produced per unit of finished cement varies even more, depending on cement composition
(e.g. content of clinker and non-clinker ingredients), manufacturing efficiency, etc. Recent
data on global CO2 emissions from cement manufacture give an overall average of 0.88 t/t.
The same data indicate a value for Europe of about 0.63 t/t. These data imply that about 2 Gt
of CO2 per year are currently emitted directly to the atmosphere due to cement manufacture.

The pressure to reduce energy consumption and CO2 emissions during cement manufacture
has led the industry to increase the extent to which Portland clinker is substituted in
conventional cements by other ingredients that are currently approved in the existing norms,
such as granulated blastfurnace slag (ggbs), pulverized fuel ash (pfa), natural pozzolans and
limestone. However, there have until recently been few serious attempts to develop novel
cements based on alternative clinkers with intrinsically lower manufacturing CO2 emissions
than conventional Portland cement clinkers.
A number of alternative cements have been proposed to deal with perceived CO2 and energy
problems3,4,5. However, as well as demonstrating appropriate physical properties and
durability when used in concrete, any potential replacement cement must be based on
minerals available in quantities comparable to the demand, and well-distributed world-wide.
Cements based on significantly less abundant minerals are unlikely to be produced in
quantities large enough to have much impact on global CO2 emissions.

Some of the most promising alternative cementing systems for general concrete applications
at ambient temperatures currently appear to be those based at least in part on calcium sulfates,
the availability of which is increasing due to the widespread implementation of sulfur dioxide
emission controls. These include calcium sulfoaluminate (CSA) and belite-calcium
sulfoaluminate-ferrite (BCSAF) cements and similar systems that make good use of the
potential synergies between hydrated calcium silicates, sulfates and aluminates. Some such
cements have been normalised in China under the generic name “the Third Cement Series”.

In this paper we report some encouraging preliminary results obtained on two novel
cementing systems of this general type:

• CSA-rich clinkers blended with ggbs and other non-clinker ingredients


INTERNATIONAL CONFERENCE ON SUSTAINABILITY IN THE CEMENT AND CONCRETE
INDUSTRY – Lillehammer, Norway, 16 – 19 September 2007

• BCSAF clinkers which can be made in conventional OPC kilns

BELITE-RICH CEMENTS

Belite-rich cements can be made by burning mixtures of limestone and clay in a similar
process to that used for OPC manufacture. The theoretical energy requirements and process
CO2 emissions for the manufacture of belite-rich cements are lower than that for OPC (the
main hydraulic component of which is alite, an impure form of C3S).
The formation of a high percentage of alite in clinker requires that a finely-ground and
homogenised mixture of raw materials be heated to a minimum temperature of about 1400oC
in the rotary kiln. However, belite, C2S, is formed rapidly at above 1200oC if the raw
materials are sufficiently finely ground and well-mixed, so cements based mainly on belite
can generally be manufactured at significantly lower kiln temperatures.. Belite-based cements
have a further advantage over OPC in that the amount of CO2 produced by decarbonation is
reduced. This is because the CaO content of belite (65.1% by weight) is lower than that of
alite (73.7% by weight). In fact, it is this lower CaO content that really reduces the thermal
energy required to make belite, relative to alite. This is because the decarbonation of
limestone is highly endothermic, and actually accounts for the majority of the fuel
consumption in a modern energy-efficient cement kiln system. Differences in maximum
burning-zone temperature have only an indirect effect on kiln thermal efficiency. [3]
Belite-rich cements can produce concretes with very good long term properties. However,
strength development is generally very slow in comparison with alite-rich Portland cements
due to the inherently slow hydration of the usual belite phase (β-C2S). In order to produce
cements suitable for most modern applications it is therefore necessary to either produce a
more reactive form of belite or to add a more reactive component to contribute to the early
age strength development.
The presence of Fe2O3 in the raw meal can lead to the formation of ferrite (C4AF) and to the
partial substitution of Al2O3 in other alumina-rich phases such as calcium sulfoaluminate.
The inclusion of higher levels of Fe2O3 increases the range of raw materials that can be used
in manufacture and so has the potential to reduce the cost. Fe2O3 also usually acts as a flux in
the clinkering process, which can help reduce the kiln residence time.
The compositions of belite-based cements can be altered through the inclusion of reactive
phases, such as calcium sulfoaluminate, C4A3s (mineral name: ye’elimite), that increase the
early strength. The reactive phase C4A3s (in some cases together with Cs and/or C4AF)
hydrates to produce ettringite as the main hydrate phase responsible for the early strength.
The belite component hydrates more slowly and is responsible for the long-term strength.
C4A3s can be formed in a cement kiln at temperatures between about 1000oC and 1300oC.
The production of 1 tonne of C4A3s generates only 216kg of CO2 from limestone
decarbonation if one assumes that its sulfate originates from calcium sulfate in the raw mix.
(If this sulfate originates from the combustion of sulfur in fuel and its reaction with lime, then
this figure increases slightly, to 288kg of CO2per tonne of C4A3s; but it is still a low value.)
A simple calculation for a belite-sulfoaluminate cement (assumed to contain 38% belite and
35% C4A3s together with calcite calcium aluminoferrite and calcium sulphate) suggests that
limestone decarbonation would only produce about 300 kg CO2 per tonne of cement.
INTERNATIONAL CONFERENCE ON SUSTAINABILITY IN THE CEMENT AND CONCRETE
INDUSTRY – Lillehammer, Norway, 16 – 19 September 2007

However, CO2 emissions arising from energy consumption must be added to these figures.
Whilst it is not possible to accurately determine CO2 savings arising from any reductions in
energy use prior to carrying out manufacture on a large scale it is reasonable to assume that,
within limits, energy use is proportional to CaCO3 content of the raw feed. Consequently, if
such clinkers can be made in modern energy efficient (preheater) kiln systems, overall CO2
emissions can be assumed to be reduced roughly in proportion to the reduction in process CO2
emissions.

EXPERIMENTAL

An experimental programme was carried out to assess the performance of concretes made
using various CSA-based cements. The mix design used in each case was as follows:

Total binder content: 300kg/m3


Free water: binder ratio: 0.55
Total aggregate: cement ratio: 6.1:1
20-10mm Thames Valley 35%
10-5mm Thames Valley 25%
5-0mm Thames Valley 40%

No additives were used. Concretes were subjected to a standard curing regime involving 24
hours curing in moulds under damped Hessian prior to storage in the following environments:
• Water at 20oC
• Water at 5oC
• Water at 38oC
• Air (20oC, 65% RH)
• External sheltered
• External unsheltered
• 4% CO2, 65% RH, 20oC (accelerated carbonation)

Compressive strength determinations were carried out on 100 mm cubes in accordance with
BS1881: Part 116 (6). The hydrated phases present in the samples were identified by X-ray
diffractometry, with a Siemens D500 diffractometer using Cu Kα radiation and operating at
40 KV and 30 mA. Data were accumulated over one scan of 2θ between 5o and 50o.
Assignments of lines were made by comparisons with JCPDS files. Conduction calorimetry
was carried out using a Wexham isothermal conduction calorimeter.

Carbonation depth was measured on 75x75x200mm prisms made using the same mix designs
as used for compressive strength development. Specimens for accelerated carbonation were
stored in water to 28 days followed by 28 days conditioning at 20oC and 65% RH prior to
testing (carbonation occurred over this period, as shown by the carbonation depth at 0 days).
The samples were then exposed to a carbon dioxide enriched atmosphere with a CO2 level of
4% at 20oC and 65% RH. Carbonation depths were measured at 2-weekly intervals as
INTERNATIONAL CONFERENCE ON SUSTAINABILITY IN THE CEMENT AND CONCRETE
INDUSTRY – Lillehammer, Norway, 16 – 19 September 2007

described above. Specimens for natural carbonation were cured under damp Hessian and
polythene to 1 day prior to placing in the following exposure conditions:
a. Indoors at 65%RH and 20oC
b. Outside sheltered
c. Outside unsheltered
Carbonation depths were determined by spraying freshly fractured surfaces of concrete
specimens with a phenolphthalein indicator solution and measuring the depth of the coloured
region at 5 points along each edge of the specimen before averaging.

CSA-GGBS BLENDS

The properties of concretes made using a range of CSA cements were studied. The
compositions of some of the cements used are shown in Table 1. Theoretical CO2 savings
relative to pure PC concretes depend on the composition but can be over 70% for the
compositions studied.

Table 1. Compositions of CSA cements


Oxide content (wt%)
Oxide Cem A Cem B Cem C Cem D B2
SiO2 8.35 4.86 8.19 5.71 9.9
Al2O3 25.6 34.2 24.5 35.9 33.2
Fe2O3 2.84 2.46 2.70 2.47 1.0
CaO 42.0 40.7 42.4 40.9 47.0
SO3 13.8 12.0 13.1 9.30 7.9

XRD analyses showed that the cements were composed of various proportions of ye’elimite,
belite, anhydrite and gypsum with small amounts of calcite and possibly tricalcium aluminate.

Studies have included compressive strength development and durability to 2 years. The CSA
cements were used neat and in blends with other components such as ggbs, pfa and anhydrite.
Conduction calorimetry outputs on cements A to D and B2 are shown in Figure 1.
INTERNATIONAL CONFERENCE ON SUSTAINABILITY IN THE CEMENT AND CONCRETE
INDUSTRY – Lillehammer, Norway, 16 – 19 September 2007

500

450

400

350

B2 batch 1075
300 Cement A
Cell output mW

Cement B
250 Cement C
Cement D
200

150

100

50

0
0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0
Time h

Figure 1. Conduction calorimetry outputs for cements A to D, and for B2 (in each case the
cell contained 30g cement mixed with 18.6g water)
Early age compressive strength data for concrete made using neat CSA cements in water at
20oC are shown in Figure 2. 90 day strengths are comparable with otherwise equivalent
concrete made using a typical British OPC (type CEM I 42.5R).

Strength development in CSA cements blended with ggbs and anhydrite are shown in
Figure 3. From these results it is clear that CSA-rich clinker on its own is not a good activator
for ggbs. However, combinations of CSA with calcium sulfate show good strength
development properties when combined with ggbs (although the composition of the CSA is
important in determining this). The effects of curing regime on compressive strength at 180
days are shown in Figure 4.

60

50
Compressive strength/MPa

40

30 B2 only

PC only
20
Cement A

10 Cement D

0
0 10 20 30 40 50 60 70 80 90 100
Age/days

Figure 2. Compressive strength development in concretes made from “pure” CSA-based


cements, compared to “pure” OPC (cement content = 300kg/m3; w/c = 0.55)
INTERNATIONAL CONFERENCE ON SUSTAINABILITY IN THE CEMENT AND CONCRETE
INDUSTRY – Lillehammer, Norway, 16 – 19 September 2007

90

80

70
Compressive strength/MPa

60

50
B2 only

40
50% B2; 50% Slag

30
30% B2; 20% Anhydrite; 50% Slag

20
42% B2; 30% ggbs; 28% Cs

10
PC only

0 50% PC; 50% ggbs


1 10 100 1000
Age/days

Figure 3. Compressive strength development in concretes made from CSA/ggbs/anhydrite


blends, compared to a PC/slag blend (cement content = 300kg/m3; w/c = 0.55)

90
PC
80
B2
70 PC/ggbs
Compressive strength/MPa

30 B2/50 ggbs/ 20Cs


60
42 B2/30 ggbs/ 28 Cs

50

40

30

20

10

0
20oC water 20oC air 38oC water 5oC water

Figure 4. Compressive strengths in different environments at 180 days


Concrete tests of this type of blend show no significant expansion in water over 9 months and
a rate of carbonation higher than OPC but not extreme7. Longer term tests are ongoing.
Precast manufacturing trials have also proved to be promising.

Although certain CSA/anhydrite/slag blends give promising results, this raises the issue of the
current limited global supplies of high-CSA clinkers and of good quality blastfurnace slags.
INTERNATIONAL CONFERENCE ON SUSTAINABILITY IN THE CEMENT AND CONCRETE
INDUSTRY – Lillehammer, Norway, 16 – 19 September 2007

LAFARGE’S NOVEL BELITE-CSA-FERRITE (BCSAF) CEMENTS

Lafarge has recently developed a novel type of cement based on an activated belite/CSA/
ferrite clinker interground with anhydrite. It can be manufactured from a wide range of raw
materials in conventional Portland cement kilns. With non-activated clinker, rapid setting and
hardening due to rapid consumption of C4A3Š and anhydrite and formation of ettringite
usually occur, with belite hydration being delayed. However, certain combinations of minor
elements allow significant activation of the belite (by formation of the ά phase), while C4A3Š
hydration is retarded slightly, giving better set and workability control. The ferrite phase also
appears to contribute to strength development. With these modified clinkers, belite hydration
is significant even at one day. Manufacture of such clinkers is predicted to give 20-25% less
CO2 emissions than Portland cement clinker, and similar levels of CO2 savings are expected
for cements made from such clinkers. The results shown here were obtained with a simple
BCSAF cement (B3) containing only clinker plus 10% calcium sulfate, but the use of these
cements in more complex blends with supplementary cementitious materials such as ggbs is
currently being investigated by Lafarge and will certainly lead to even greater CO2 savings.

Compressive strength development


Strength development for B3 in moist-cured concrete is shown in Figure 5 and is very similar
to the otherwise equivalent OPC concrete control. 90-day compressive strengths on storage in
water at 38oC and at 5oC were also similar to those of the PC controls. Longer term strength
development and durability studies are under way.

50

45

40
Compressive strength/MPa

35
PC only
30

25

20 B3 only

15

10

0
0 10 20 30 40 50 60 70 80 90 100
Age/days

Figure 5. Compressive strength development in equivalent concretes made using


Lafarge’s BCSAF cement (B3) and PC (cement content = 300kg/m3; w/c = 0.55)

Dimensional stability
75 x 75 x 200mm concrete prisms were prepared (with steel inserts cast-in to each end
facilitate dimensional measurements) using the mix design outlined above. The prisms were
assessed for dimensional stability under the following conditions:
1. Storage in water at 20oC
2. Storage in air at 20oC and 65% RH (after 28 days water curing at 20oC)
INTERNATIONAL CONFERENCE ON SUSTAINABILITY IN THE CEMENT AND CONCRETE
INDUSTRY – Lillehammer, Norway, 16 – 19 September 2007

3. Storage in water at 20oC following heat curing at 90oC for 4 hours

The results are shown in Figure 6. Results for PC concrete stored under similar conditions are
shown in Figure 7.

0.025
B3 Dry after water 20oc

0.02 B3 Heat cure


Series1
0.015
% expansion

0.01

0.005

0
0 5 10 15
-0.005 Time/weeks

-0.01

Figure 6. Dimensional stability of B3 concrete

0.025 PC Water, 20oC

PC Dry after water 20oc


0.02 PC Heat cure

0.015
% expansion

0.01

0.005

0
0 5 10 15
-0.005 Time/weeks

-0.01

Figure 7. Dimensional stability of OPC concrete

Carbonation
B3 concrete carbonated more rapidly than the OPC control under accelerated carbonation
conditions. Carbonation depths of 6mm and 3mm were measured for B3 and OPC concrete
respectively after 91 days. However, there was little difference in the rate of natural
carbonation in dry and external sheltered environments after 91 days. Longer term tests are
underway. Future tests will examine steel corrosion risks directly.
INTERNATIONAL CONFERENCE ON SUSTAINABILITY IN THE CEMENT AND CONCRETE
INDUSTRY – Lillehammer, Norway, 16 – 19 September 2007

CONCLUSIONS

It is difficult to change cement manufacturing technology to greatly reduce CO2 emissions


because few alternative raw materials are widely available in sufficient quantities. Even if the
materials are available, transportation costs can be high.

However, our results show that it is possible, under the right conditions, to manufacture
cements having equivalent performance to Portland cements but with significantly lower CO2
emissions per unit of clinker, which implies also the possibility for lower CO2 emissions per
unit volume of concrete.

Cements based on C4A3Š plus ferrites, calcium sulfates and either ggbs or activated belite are
a promising option. They can tolerate high sulfate contents and hydrate to form mainly
ettringite, C-S-H & AFm phases. Preliminary concrete tests of two alternative approaches to
this have shown promising strength and durability results, but much more work is needed to
establish sufficient data to allow for normalisation of such cements and their acceptance in
general construction applications. In developing a new cement for large scale use a number of
key objectives would need to be met:

1. CO2 emissions and energy consumption from manufacture needs to be as low as


possible. Other emissions (e.g. NOx and SOx) also need to be tightly controlled.
2. The cement must be fit for purpose when used in concrete, mortar, etc. For example:
• Concrete made using it needs to have handling characteristics that are appropriate
for a high-volume construction material. It must be consistent with H&S
legislation, be readily mixable using conventional concrete mixing equipment,
have handling and setting times that allow easy placement, but yet gain strength at
a reasonable rate (under typical curing conditions) so to allow subsequent work to
progress rapidly.
• Characteristics such as strength development, durability, etc., must be comparable
to those of existing construction cements (particularly Portland cements).
3. Raw materials must be cheap and readily available locally. Ideally waste and by-
product materials from other sectors should be consumed in making such cements.
4. Other processing costs also need to be acceptable, such that the final cost of such
cements is low enough to be competitive as a means of reducing cement-related
industrial CO2 emissions, (as opposed, for example, to the proposed separation of CO2
from cement plant exhaust gases and its liquefaction for underground sequestration).

Whilst it is to some degree possible to tailor the properties of a cement to a particular


application, the aim here is to develop a material for bulk use as with Portland cement.
Consequently, appropriate codes and standards for a new class of cements will need to be
developed. This will require a major investment in collecting and analysing appropriate data
and developing the codes and standards themselves.
INTERNATIONAL CONFERENCE ON SUSTAINABILITY IN THE CEMENT AND CONCRETE
INDUSTRY – Lillehammer, Norway, 16 – 19 September 2007

REFERENCES

1 P Livesey, Challenges for the cement industry, p321 Concrete for environmental
enhancement and protection, ed. RK Dhir and TD Dyer, Spon, London (1996).
2 European cement association (Cembureau); "Energy is a sensitive factor in cement
manufacture"; www.cembureau.be, 2000.
3 E Gartner, “Industrially Interesting Approaches to ‘Low CO2’ Cements.” Cem. Concr.
Res. 34 [9] 1489–1498 (2004).
4 K Quillin, ‘Low energy cements, BRE Report 421 (1999).
5 CD Lawrence, ‘The production of low energy cements’, in Lea’s Chemistry of Cement
and Concrete, 4th Edition, Ed. PC Hewlett, Arnold, London (1998).

6 BS 1881: Part 116: 1983: Method for determination of compressive strength of concrete
cubes, British Standards Institution, London (1983).
7 Low carbon belite-calcium sulfoaluminate cements, to be published

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