QCL Group Technical Notes Page 1

The Role of Gypsum in Cement March 99

THE ROLE OF GYPSUM
IN CEMENT
Gypsum is a soft, transparent or translucent mineral composed of crystallised calcium sulphate (CaSO
4
), found
naturally primarily in sedimentary deposits. I t is used in the manufacture of wall boards, paper, paints, plasters and
cement.
Gypsum is added to Portland cement to regulate the otherwise extreme setting reaction which occurs in the presence of
water. The gypsum content of cement is expressed in terms of its sulphate (SO
3
) content. Sulphate is a readily
determined measure of gypsum in cement.
Portland cement usually contains around 5% gypsum, which is equal to approximately 2.1% SO
3
. The maximum SO
3
content allowed by AS 3972 Portland and Blended Cements is 3.5%.
As well as influencing the setting time, gypsum also has an influence on other properties of cement. The more
important of these properties are strength, strength development and volume stability. Gypsum also influences the
grindability of the cement, which is the grinding energy required to produce cement.
THE EFFECT OF GYPSUM ON
SETTI NG OF CEMENT
The setting of cement involves the reaction of clinker
minerals with water, to form a system of interlocking
crystals, which lock the material together.
The setting of cement is primarily due to the reaction of
tricalcium aluminate (C
3
A), which is the most reactive
of the four clinker minerals present in cement. The set
regulating action of gypsum is due primarily to its
reaction with C
3
A.
In the absence of gypsum, the reaction of C
3
A with
water is very rapid. The C
3
A is converted to calcium
aluminate hydrate (4CaO.Al
2
O
3
.19H
2
O), which forms
interlinking bridges of solid material between the
cement particles. These interlinking bridges reduce the
mobility of the cement particles and produce a firm
structure, which results in setting of the cement mixture.
This rapid setting is called a flash set and is irreversible.
The presence of gypsum in cement slows the reaction of
the C
3
A. When mixed with water, gypsum dissolves and
reacts with C
3
A to form ettringite (3Ca0.Al
2
0
3
.3CaSO
4
.
32H
2
0). This ettringite is initially formed as very fine-
grained crystals, which form a coating on the surface of
the C
3
A particles (Figure 1).
These crystals are too small to bridge the gaps between
the particles of cement. The cement mix therefore
remains plastic.
After the initial hydration reactions of cement, a
dormant period occurs during which the rate of
hydration of cement is greatly reduced. During this
dormant period, ettringite crystals continue to grow and
eventually are large enough to impede the mobility of
cement particles. At this stage setting occurs.
Figure 1: First stage - formation of a thin cover of
ettringite on the C
3
A surface
Figure 2: Second stage - a further amount of ettringite
is formed on the C
3
A surface
A full explanation for this dormant period is still a
matter of some conjecture. Different mechanisms have
been proposed by researchers. The classical explanation
is that the ettringite coating which covers the cement
particles reduces contact between the cement and water
thereby retarding hydration. However, this theory is
being modified, as more data becomes available.
THE EFFECT OF GYPSUM
SOLUBI LI TY
QCL GROUP
QCL Group Technical Notes Page 2
The Role of Gypsum in Cement March 99
The rate of the reaction between C
3
A and gypsum
depends on the availability of dissolved gypsum in the
mixing water.
Gypsum (CaSO
4
2H
2
0) is a chemically stable naturally
occurring mineral of moderate solubility. When gypsum
is heated however, it dehydrates and is converted to
plaster of paris (CaSO
4
.H
2
0) and at higher
temperatures anhydrite (CaSO
4
). Both these
dehydration products are significantly more soluble than
gypsum.
The dehydration of gypsum occurs at relatively low
temperatures: 100
o
C to 160
o
C. Such temperatures can
occur during the cement grinding process. Strict
temperature controls are therefore exercised during the
grinding process.
Sustained high temperatures during the grinding of
cement can result in the formation of significant
quantities of plaster of paris and anhydrite. These
minerals react readily with water to recrystallise as
gypsum. This process is termed a false set, which,
contrary to a flash set, is reversible. Extended or further
mixing causes the stiffened cement paste to revert to a
plastic state.
OPTI MUM GYPSUM CONTENT
The optimum gypsum content for a cement is dependent
on a number of factors, chief among these are the C
3
A
content, the reactivity of this C
3
A (which is a function of
process, conditions, and trace elements present such as
alkalis, strontium, etc), the solubility of the gypsum, and
milling temperatures. The effect of gypsum on the
setting time of a cement is demonstrated in Figures 3
and 4. The effect of C
3
A content is also shown.
STRENGTH AND VOLUME STABI LI TY
The addition of gypsum to cement increases the strength
obtained and reduces shrinkage. However, the addition
of excessive amounts of gypsum causes expansion to
occur, which is why cement standards place a limit on
the sulphate content.
The level of gypsum at which expansion becomes a
problem is dependent on the C
3
A content and fineness
of the cement. Figures 5 and 6 show the effects of
gypsum on compressive strength and shrinkage.
Figure 3: Variation of setting time with gypsum content
(6.2% C
3
A)
Figure 4: Variation of setting time with gypsum content
(13.2% C
3
A)
Figure 5: Effect of gypsum content (as SO
3
) on
compressive strength
Figure 6: Effect of gypsum content (as SO
3
) on
shrinkage