Optimization of Cement Sulfate

Part 2 - Cement with Admixture

MC171

INTRODUCTION set time is strongly affected by the free water content (determines
how much hydrates must form before particles become interlocked)
William Lerch published a paper in 1946 on the optimum sulfate and both the aluminate and the Alite rate of hydration.
content in Portland cement, which demonstrated that the optimum
sulfate content with respect to mortar strength correlated closely The aluminate and Alite compete for water for their hydration.
with heat of hydration measured by isothermal calorimetry, Since aluminate is much more reactive, it is critical to have enough
and also with the length change of mortar bars stored in water. sulfate available to retard the aluminate. Sulfate must first dissolve
Lerch concluded that a Portland cement with close to optimum before it can react with aluminate to form ettringite, which coats
sulfate content would display a calorimetry heat profile with the the surface and retards the aluminate hydration. If not enough
time of sulfate depletion occurring after the main silicate hydration sulfate is available to slow down the aluminate hydration, loss of
peak. The results of Lerch were reviewed and it was showed that workability or even flash set may occur as the aluminate hydrates
calorimetry might be used to consider optimum sulfate levels also formed rapidly consume free water. Since the aluminate hydrates
for mixture with cement and admixture. also tend to coat the Alite, excess aluminate hydrates may retard
and partly prevent the onset of the strength giving Alite hydration.
INTRODUCTION
CALORIMETRY HEAT PROFILES FROM HYDRATING
Sulfate is added to clinker in the manufacture of Portland cement PORTLAND CEMENT IN PRESENCE OF ADMIXTURE
for the purpose of retarding the hydration of the aluminate phase.
Codes such as ASTM C150 and EN197 regulate the maximum Fig. 1 shows an example of the effect of a typical water-
sulfate expressed as SO3 with respect to durability, but no SO3 reducing admixture on the hydration of a Portland monitored
minimums are assigned. An extensive study by William Lerch /1/ at room temperature by an isothermal conduction calorimeter.
used isothermal calorimetry to study the influence of gypsum The Portland cement by itself had a slightly higher than optimum
addition rates to range of commercial clinkers on the hydration sulfate content, as seen by the sulfate conversion peak appearing
performance of corresponding Portland cements in terms of several hours after the maximum of the main silicate hydration
strength development and dimensional stability. It was concluded peak. As the water-reducing admixture was added to the
that the optimum sulfate content for maximum strength usually mixture at increasing dosages, the aluminate reactivity increased
correlates with minimum dimensional change during water while the main strength giving silicate hydration was retarded.
storage. The optimum sulfate content was easily identified by a As a consequence, note how the sulfate depletion peak appeared
calorimetry heat profile. closer and closer to the maximum of the main silicate hydration
peak. Eventually, the sulfate depletion peak appeared before
Admixtures in general may have an impact both on the activity of the now strongly retarded silicate hydration peak, when a strong
the aluminate phase (which needs sufficient sulfate to be retarded overdose of admixture was used.
enough to avoid slump loss) and the solubility of sulfate (which 4.00
impacts how available the sulfate is to react with aluminate).
Water/cement ratio, 0.5, 23 ºC
As a result, most admixtures have some impact on the optimum 3.50 Increased
mix water addition
Second Peak: Power (mW/g)

admixture
SO3 of a mixture compared to the same mixture without 3.00
dosage

admixture. Consequently, a given cement that has sufficient SO3

2.50
without admixture may experience a lack of sulfate in presence
of admixture. This is especially true for some highly reactive 2.00
Acc.
class C fly ashes, due to their content of reactive aluminate, and 1.50
aluminate

for chemical admixtures that accelerate the aluminate hydration.

1.00
HYDRATION PHENOMENA GOVERNING SET AND STRENGTH 0.50 Sulfate depletion
DEVELOPMENT
0.00
0 2 4 6 8 10 12 14 16 18 20 22 24
Portland cement has four major phases, aluminate “C3A”, Alite
Time (hrs)
“C3S”, Belite “C2S”, and ferrite “C4AF”. The aluminate ids the most
reactive phase, and therefore has the largest impact on workability Figure 1. Effect of progressively increased admixture dosage on calorimetry
as it consumes large amounts of water upon hydration. The Alite response. Note how the strength giving silicate hydration peak appeared to
is the second most reactive phase, with strong impact on set and be retarded, both in size and timing, as the strong overdose of admixture
accelerated the aluminate hydration, which further retarded the silicate
strength development. Set occurs when enough hydrates has
hydration. The cement used meets the specification for ASTM Type I and II
formed to interlock particles and restrict their flow. Therefore, the Portland cement, 2.9% SO3, BSA 380 m2/kg.

1 MC171
LABORATORY SCREENING OF THE STABILITY OF CEMENT – 6.00
5.50
ADMIXTURE COMBINATIONS
5.00

Second Peak: Power (mW/g)

Mix with admixture

Based on the results shown in Fig. 1, it was concluded that the tested 4.50 and 0.5% SO3 added
as calcium sulfate
4.00
cement-admixture combination appears to be “robust” because a hemihydrate

3.50
50% admixture overdose was not enough to significantly alter the Insufficient
3.00
cement hydration profile. As a rule of thumb, one should always aluminate control
in “unstable” mixture
2.50 Retarded silicate
test a candidate cement-admixture combination at an overdose 2.00
hydration in

of admixture, because the result will indicate if a mixture is close

“Unstable” mixture
1.50
to an “out-of-balance” situation or not. If an intended mixture is 1.00
close to being “out-of-balance”, one should look for a more stable 0.50
mixture design. Mixtures close to “out-of-balance” typically result 0.00
in undesired high variability in concrete setting time, strength 0 2 4 6 8 10 12 14 16 18 20

development, and sometimes also premature stiffening as a result Time (hrs)

of not properly controlled aluminate hydration. Since cement has Figure 2. Soluble sulfate test on an “unstable” cement-admixture
an inherent natural variability in composition and reactivity, and combination by monitoring the timing of the main silicate hydration
concrete conditions vary, it is very important to design “robust” peak. An ASTM Type A Water reducing admixture was used according
to the manufacturers recommendations (0.4% s/s). Green plot is the
mixtures that can tolerate minor variations in reactivity without the “unstable” mixture; Yellow plot is the same mixture with 0.5% SO3 added
mixture being put “out-of-balance”. to the cement as plaster. The cement used meets the specification for
ASTM Type I Portland cement, 2.3% SO3, BSA 370 m2/kg.
It would be impossible for a cement producer to test all their
cements for all possible admixture combinations. Cement is used CONCLUSION
in many different processes, cement contents, and temperatures,
making it impossible to optimize the sulfate content for all Calorimetry can be a very useful tool for screening cement-
situations. Furthermore, restrictions imposed by ASTM, states, admixture combinations with respect to hydration stability.
DOT’s, AAHSTO; etc often limits the total SO3 allowed in cement. Repeated tests are recommended, as single tests can usually not
On the other hand, one can select a few most common admixture tell if a given mixture design is very sensitive to changes or not.
combinations that represent the local marketplace, and then use
Most aspects of cement hydration and performance with
these combinations for screening cement. Such screening should
admixture involve heat evolution, and can therefore be monitored
be done whenever there is a known change in cement composition
by calorimetry. Certain processes however, such as excess air
or process, or when concrete producers are developing new
entrainment and false set, involve so little heat relative to the
mixture designs.
overall process, that calorimetry is not a suitable screening tool.
Likewise, it would be impossible for concrete producers to test
Loss of workability or slump in concrete can to some extent be
all incoming cement loads for all admixture combinations used.
assessed by calorimetry on cement paste, by monitoring the
However, screens would be recommended whenever there is a
heat associated with aluminate hydration before time of placing.
known change in type or amount of the materials used, or when
Note however that calorimetry results reflect chemical aspects
there is a significant change in concrete curing temperature.
only. Any physical effects such as absorption on aggregate fines
TEST FOR THE EFFECT OF ADDITIONAL SOLUBLE SULFATE cannot be assessed by calorimetry tests only. Since the heat
evolution measured in an externally mixed sample does not
Unstable cement–admixture combinations usually display a become quantitative until 10-15 minutes after inserting the sample
sulfate depletion peak appearing before or at the same time as into the calorimeter, one must use some caution when comparing
the main silicate hydration peak. It is then recommended to run heat evolution during the first 15 minutes. Slump loss occurring
a separate test series with additional soluble sulfate added to the more than 15 minutes after initial mixing would be detectable as
cement. The added sulfate test will help to confirm the location an increased heat evolution only if it is induced by an acceleration
of the sulfate depletion peak, which is sometimes difficult to of the aluminate hydration.
identify if it is completely overlapping the main silicate peak. The
added sulfate test would also prevent any “unknown” hydration REFERENCES
peaks (such as early aluminate hydration induced by accelerating
1. Lerch, William. “The influence of gypsum on the hydration and
admixtures) from being mistaken for a sulfate depletion peak.
properties of Portland cement pastes”, Proceedings, Vol. 46,
Sulfate is usually added in the form of calcium sulfate hemihydrate
of the American Society for Testing Materials, 1946
(plaster), since this is the most soluble form of calcium sulfate.
Fig. 2 shows an example of a sulfate test on a cement-admixture 2. Sandberg, Paul. “The use of Isothermal Calorimetry to
combination that appears to be unstable. optimize cement sulfate. Part 1 - Cement without admixture.
Internal document, Grace Construction Products

For more information or to request a product quote, please visit

www.tainstruments.com/ to locate your local sales office
information.

© TA Instruments 2 MC171