Sulphate optimisation: the role

of gypsum in cement

Matteo Magistri
Cement course 2018 – Session 8
“Gypsum” is the name of a naturally occurring mineral mainly composed of
calcium sulfate, more precisely di-hydrate calcium sulfate (di-hydrate means
that two molecules of water are present in the crystal structure):

CaSO4·2H2O

Sulfate ion Calcium Water

SO42- ion Ca2+ molecules H2O
“Gypsum” is quarried (or obtained as by-products of other industries) and
added to all types of Portland cements normally produced according to all
types of international standards (EN, ASTM, ...).

The use of calcium sulfate as addition to cements was first suggested by

Scott in 1873, following early years of Portland cement development (first
patent for something similar to what is now called Portland Cement was
granted to Joseph Aspdin in 1824, first manufacturing dates back to 1871).
A very common quality control parameter for cement production is the SO3
content, usually ranging from 2.0% to 3.5%.

Formally, calcium sulfate can be considered as derived from reaction of calcium oxide
and SO3 (CaSO4 = CaO + SO3).

SO3 content generally refers to the total sulfate ion contained in cement,
coming from gypsum and clinker (and sometimes from other mineral
additions).

Typical SO3 content for CEM I:

5% gypsum: corresponds to 2.2% SO3

95% clinker: can give additional 0.5-1.0% SO3
Total: 2.7-3.2% SO3
Portland cement, when mixed with water for preparation of mortars and
concrete, should give a fluid mix, set in a reasonable time, develop good
mechanical strengths and retain dimensional stability for a long time.

In fact, the purposes of sulfate (gypsum) addition to cements are the

following:

1. Control of workability

2. Control of setting time

3. Control of mechanical performances

4. Control of shrinkage/expansion
Workability: the sulfate addition allows correct workability of cement mortars
and concrete. Pure clinker (although reacting with water to form hydration
products) would not have any possibility of being casted, processed and used.

Pure ground clinker: Clinker + gypsum: homogeneous

immediate stiffening mixing and good workability when
when mixed with water mixed with water
Setting time: a minimum sulfate content is needed to control setting time.
Usually, at least 2% SO3 (corresponding to around 4.0% natural gypsum)
allows avoiding early stiffening, but too much sulfate in form of hemi-hydrate
may promote false set.
Mechanical performances: the sulfate addition strongly influences the
hydration of clinker and the development of mechanical performances (usually
measured as compressive strengths in mortar/concrete): concept of optimum
gypsum.
Shrinkage/Expansion control: shrinkage and expansion normally refers to
dimensional variation of objects made with Portland cement based mortar or
concrete.
Shrinkage/expansion can be related to evaporation of water from concrete (e.g.
drying shrinkage) or to the formation of lower density (= higher volume by
mass unit) hydration products (e.g. DEF - Delayed Ettringite Formation).
The upper limit of SO3 content in all standard referring to cements is related to
the risk of destructive expansion.
Before discussing the role of gypsum during cement hydration, let’s fix some
main points:

1) Calcium sulfate dissolves and supplies sulfate ions to mixing water during
cement hydration, starting immediately when cement is mixed with water:

CaSO4 = Ca2+ + SO42-

2) Different forms of calcium sulfate exist, depending on the water content of

crystals (2H2O, 0.5H2O, no H2O). Natural gypsum may be converted to other
forms by heating (e.g. during cement grinding).

3) Different forms of calcium sulfate differ from the point of view of dissolution
kinetics: the rate of sulfate supply to mixing water may be strongly different.

4) SO3 level only describes the total sulfate in cement, but it does not give
indication on the form of calcium sulfate.
Cement hydration: the sum of all the chemical reactions that take place when
cement is mixed with water. It is important to consider hydration from both
performances/macroscopic level and chemical/microscopic level.

+
Macroscopic point of view: when cement,
sand/gravel and water are mixed together, a
more or less fluid mix is obtained. After
casting in frameworks, it gradually
increases in viscosity and gains
mechanical performances until frameworks
can be removed. It carries on hardening
more or less quickly during first 28 days from
mixing.
Microscopic point of view: when cement,
sand/gravel and water are mixed together,
chemical compounds contained in cement
dissolve in water and release ions, that
combine in different chemical compounds
(hydration products). The cement/water
mix is progressively converted to a mix of
solid substances that bind together
aggregates and sand.
Isothermal calorimetry is a widely used analytical tool to investigate cement
hydration. It shows the rate of heat evolution per mass unit (measured in
mW/g) in function of time.
24 h: strengths development
proceeds even if no heat
development is noticeable

Plastic phase: the mix is still fluid, Setting and hardening: viscosity
although slowly increasing increases faster, development of
viscosity. mechanical strengths.
Heat evolution is related to several chemical reactions that take place in
parallel during cement hydration:

Dissolution of C3A: 3CaO·Al2O3 + 6H2O = 3Ca2+ + 2Al(OH)4- + 4OH-

Dissolution of gypsum: CaSO4 = Ca2+ + SO42-

Fluid
Dissolution of C3S: 3CaO·SiO2 + 3H2O = 3Ca2+ + H2SiO42- + 4OH- mix

Dissolution of C4AF:
4CaO·Al2O3·Fe2O3 + 10H2O = 4Ca2+ + 2Al(OH)4- + 2Fe(OH)3 + 6OH-

Precipitation of aluminate hydrates, C-S-H, Ca(OH)2:

aCa2+ + bH2SiO42- + cOH- = dC-S-H + eCa(OH)2 Hardened

mix
fCa2+ + gAl(OH)4- + hOH- + 3SO42- = iC-A-H + C3A·3CaSO4·32H2O
Let’s consider early hydration reactions: dissolution of gypsum and aluminate
phases.

Dissolution of C3A: 3CaO·Al2O3 + 6H2O = 3Ca2+ + 2Al(OH)4- + 4OH-

Dissolution of gypsum: CaSO4 = Ca2+ + SO42-

Staring from calcium, aluminium and sulphate, several hydration products may
be formed, that can be divided in two main types: calcium aluminate hydrates
(C-A-H) and ettringite.

fCa2+ + gAl(OH)4- + hOH- + 3SO42- = iC-A-H + C3A·3CaSO4·32H2O

 Clinker grains: release of
Al(OH)4- and Ca2+ from
C3A

Gypsum: releases of Ca2+

and SO42-

C-A-Hs: precipitate as plates

on clinker surface

Ettringite: crystallises in form

of rods
Some key points:

1) C-A-Hs: due to morphology and composition, calcium aluminate hydrates

tend to decrease workability and promote flash set. They probably cover the
surface of C3S slowing down the water diffusion and the consequent
hydration of C3S/strengths development.

2) Ettringite: due to different morphology, it does not reduce the water

diffusion and the hydration of C3S, promoting a normal strength
development.

3) The equilibrium C-A-H/Ettringite is strictly related to availability of

sulphate, hence to calcium sulphate.

4) In addition to amount of sulphate, the dissolution kinetics (how quickly

sulphate ion is supplied to mixing water, depending on the type of calcium
sulphate) is fundamental.
 Reactivity of C3A: how quickly Al(OH)4- is released to mix water
how quickly SO42- is released in mix water

Fast C3A, slow dissolving

Slow C3A, slow
gypsum: flash set, poor
dissolving gypsum
strengths
Dissolution of gypsum:

Slow C3A, fast dissolving Fast C3A, fast dissolving

gypsum: false set gypsum
“Fast” C3A: clinker with high C3A content, presence of orthorhombic C3A,
alkalis, high cement fineness.

How can we have a general idea of C3A reactivity?

Alkalies level in the cinker/raw mix: usually expressed as equivalent sodium

oxide Na2Oeq (it represents the sum sodium + potassium).

Sulphur to alkalis molar ratio in the kiln:

- SO3/Na2Oeq > 1: excess of sulphate, probably presence of soluble

sulphates in the clinker (Na2SO4, K2SO4, ...).

- SO3/Na2Oeq < 1: excess of alkalis, probably presence of orthorhombic C3A

in the clinker.
“Fast” dissolving gypsum: de-hydration to hemi-hydrate or soluble
anhydrite. Water in gypsum can be lost due to temperature, with conversion
of gypsum in other forms of calcium sulphate:

Gypsum: normal release

of SO42- in mix water

Hemihydrate and soluble

anhydrite: fast release of
SO42- in mix water

Natural anhydrite: very

slow release of SO42- in
mix water
De-hydration of gypsum during cement grinding: mill temperature, cooling
water, residence time in the mill. Gypsum is partially converted to hemi-hydrate
- anhydrite.
How can we have a general idea of gypsum dehydration?

- Mill temperature

- Cement temperature outside the mill.

- Amount of cooling water (ball mills) or water for vibrations control (VRM).

Considering all the info on:

- Clinker mineralogy: C3A level

- Sulphur/alkalis
- Grinding conditions (temperature/water)

We can explain cement behaviour during early hydration (workability, slump

loss, water demand) and strengths development.
Gypsum and compressive strengths: sulphates have a strong influence of
strengths development of cements. Early and late strengths are maximised at
a specific gypsum content.
1909: Spiegelburg discovers a relationship between the percentage of gypsum
in cement and the corresponding compressive strenghts, thus building the
basis for the optimum gypsum approach

1929: Berger notes how different types of calcium sulphates (e.g. hemihydrate,
anhydrous) determine different values of optimum gypsum, mainly due to
different solubility kinetics

1931: The ASTM (American Society for Testing and Materials) institutes a
working group dedicated to study the effects of diverse amount of sulphates on
the properties of cements with variable C3A content

1941: Lerch begins a detailed study on the effects of gypsum, taking into
account parameters such as the heat-liberation curves, the effect of alkalies,
the fineness and chemical/mineralogical composition of clinkers.
1976: Bentur notes how the presence of gypsum is able to accelerate the
hydration of the C3S phasis; the downturn of this aspect lies in the (apparently)
weaker hydratation products

2011: Gunay, et al. using a simulation of C3S hydration show how adsorption
of sulfate on C-S-H surface modifies nucleation/growth process. Decrease of
strengths at higher gypsum content is simply related to the lower C3S content.

Key points:

1. main silicates hydration (evidenced by hydration peak as measured with

calorimetry) must proceed in presence of sulphate in mix water, as
sulphate accelerates the nucleation and growth of C-S-H.

2. Early hydration (C-A-H/Ettringite) influences C3S hydration and

strengths development.
Optimum gypsum: increase in the hydration of C3S until optimum is reached
Optimum gypsum: sulphate depletion is delayed.
Cement additives and sulphate: some of the raw materials used for cement
additives production have a chemical effect on cement hydration.

In particular, they act as accelerators of the aluminates reactions and have

an impact on all reactions involving aluminium (and iron):

- Dissolution of C3A
- Dissolution of C4AF
- Nucleation and growth of ettringite
- Nucleation and growth of C-A-H
- Sulphate depletion

If aluminates reactivity is modified, sulphate level and type may require some
modifications: this suggest the possibility of reciprocal optimisation of
sulphate and additive.
What happnes if we accelerate dissolution and reactivity of C3A through the
addition of a chemical additive? Faster reaction of C3A may require faster
dissolving gypsum.