Progress in Crystal Growth and Characterization of Materials

53 (2007) 57e77
www.elsevier.com/locate/pcrysgrow

Calcium sulphate hemihydrate hydration leading to

gypsum crystallization
N.B. Singh a,*, B. Middendorf b
b

a
DDU Gorakhpur University, Chemistry Department, Gorakhpur 273009, India
University of Dortmund, Department of Building Materials, D-44221 Dortmund, Germany

Abstract
The hydration of calcium sulphate hemihydrate (CaSO4$0.5H2O) leading to the crystallization of
gypsum (calcium sulphate dihydrate e CaSO4$2H2O) has been the subject of several investigations over
a long period and a vast amount of data is widely distributed throughout in the literature. In this review
article an overall picture of the subject is presented. The properties of the two hemihydrates (a- and b-),
their hydration characteristics, the mechanism of their hydration and the crystal growth of gypsum are discussed. Additives modify the microstructures of the hardened gypsum and reduce its strength. A probable
mechanism is discussed.
2007 Elsevier Ltd. All rights reserved.
PACS: 81.10.Dn; 81.40.z
Keywords: A1. Crystallization; A1. Hydration; B1. Calcium sulphate hemihydrate; B1. Gypsum; B1. Plaster of Paris

1. Introduction
Calcium sulphate hemihydrate commonly known as plaster of Paris is extensively used in
buildings, ceramics and medical industries. Hydration of hemihydrate is a highly exothermic
reaction and occurs as:
CaSO4 $0:5H2 O 1:5H2 O0CaSO4 $2H2 O Q
* Corresponding author.
E-mail address: dr_n_b_singh@rediffmail.com (N.B. Singh).
0960-8974/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pcrysgrow.2007.01.002

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where Q the amount of heat evolved depends on number of factors. During hydration, gypsum
crystallization takes place. When the hydration occurs in pastes, the plaster sets and develops
strength. The setting involves physical as well as physico-mechanical processes. The hardened
mass is not a compact solid, but a highly porous material with a relatively large internal surface
consisting of interlocking crystals in the form of plates and needles. The microstructure of hardened gypsum pastes affects most of the physical and engineering properties particularly its rigidity. Nowadays the addition of small amounts of chemical additives into the hydrating
hemihydrate has become a necessity in the development of new types of bonding products.
Chemical additives are now indispensable for their use in new buildings, to restore old buildings and preserve historic monuments. In fact they have become an integral part of the building
and construction industry [1]. Chemical additives may act as retarders, accelerators, thickeners,
plasticizers, or for air entrainment or as deflocculating agents.
The morphology of calcium sulphate dihydrate crystals depends on the formation conditions
and the presence and type of chemical additives. Industrial and geochemical interest has resulted in a considerable amount of research on the mechanism of calcium sulphate dihydrate
crystal growth both in the presence and absence of different types of chemical additives
[2e15]. Nevertheless despite the intensive research work during the past decades, there is still
considerable debate and uncertainty over the mechanism. The mechanism of gypsum crystal
growth during hemihydrate hydration in the absence and presence of chemical additives is discussed in this article.
2. Hemihydrates
Depending on the process of industrial production, hemihydrate occurs in two different forms
(a- and b-forms); a-form is prepared by wet method (e.g., autoclaving) and b-form is prepared
by dry methods (e.g., calcining) from calcium sulphate dihydrate [16e19]. In the laboratory
[19] b-hemihydrate is prepared from the dihydrate by heating under a low water vapour partial
pressure, i.e., in dry air or vaccum, between 45  C and 200  C whereas a-hemihydrate is
prepared from the dihydrate under a high partial pressure of water vapour, e.g., above 45  C
in acid or salt solutions, or above 97.2  C in water under pressure. The industrial dehydration
and rehydration of different calcium sulphates are shown in Fig. 1.
The two forms of hemihydrate differ in their reactivity with water and in the strength of the
hydration products. No structural differences have been reported by X-ray diffraction studies.
Infrared spectral studies also showed no significant differences between the two forms [20,21].
However according to Bushuev and Borisov [22], the a-modification crystallizes in the monoclinic form whereas the b-hemihydrate crystallizes in the trigonal form. According to Kuzel
and Hauner [23] there are no crystallographic differences, the a- and b-forms differ only in
the size and arrangement of the crystals. When the same wateregypsum ratio is used to set the
a- and b-hemihydrates, the a-hemihydrate produces a gypsum with considerably more strength
[24]. The Raman spectra of both the hemihyrates show differences that suggest structural
variations. It is possible that even monocrystalline aggregates contain regions of water molecules arranged in a different way. Structural differences between a- and b-hemihydrates could
also be detected using NMR spectroscopic investigations. Fig. 2 shows the static 1H NMR line
shapes obtained in a field of 9.4 T, which corresponds to a resonance frequency of 400 MHz,
and at a temperature of 295 K. Analogue to results from CaSO4$2H2O [25] also show a
fine structure in the static 1H line shapes. This was caused by dipolar interactions between
neighbouring hydrogen probe nuclei. The doublet at 20 kHz results from hydrogen nuclei

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59

Fig. 1. Different modifications of CaSO4xH2O (x 0.0e2.0).

that occur in pairs, i.e., isolated water molecules. The strong line at 0 kHz, in the case of the
b-hemihydrate, indicates an isolated group with more than two hydrogen nuclei. The differences in the spectra of a- and b-hemihydrates therefore clearly show the different surroundings
of the hydrogen probe nuclei and thus the differences that occur when water is incorporated into
the samples.
Lehmann [26] carried out differential thermal analysis of both the forms and found differences in the transformation temperatures. According to Follner et al. [27], there are differences
in the structures of the two forms of hemihydrate but the structures are difficult to establish.
Scanning electron microscopic pictures (Fig. 3) have shown that the a-hemihydrate
consists of well-formed transparent idiomorphic crystals with sharp crystal edges whereas
b-hemihydrate consists of flaky particles made up of small crystals. b-Hemihydrate requires
more water than the a-hemihydrate in order to obtain a paste of standard consistency because it
has a much higher specific surface area. Some of the properties of the two hemihydrates are
given in Table 1.
In order to compare the hydraulic activity of the two forms of hemihydrate, Lewry and Williamson [2] studied the hydration by using different experimental techniques. They measured
the temperature and electrical resistance changes of the paste (water/plaster, w/p 0.6) as
a function of time and found that the two hemihydrates behave in a similar way with some
differences. In Fig. 4, the induction period for a-hemihydrate hydration is shorter than that
for b-hemihydrate but subsequently the b-hemihydrate hydrates faster because of its higher surface area which provides more nucleation sites for the crystallization of gypsum.
The change in electrical resistance with the time of hydration is shown in Fig. 5. From the
figure it is clear that the reaction takes place in three stages. (i) A minimum resistance was
obtained in the first 5e10 min. This represents the point of maximum solubility of the calcium

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Fig. 2. The static 1H NMR line shapes of (a) a- and (b) b-hemihydrate, taken at a central frequency of 400 MHz and
295 K.

and sulphate ions. (ii) The resistance then increased steadily over the next 100 min and this was
due to the precipitation of the dihydrate. This can be explained by considering the densities of
reactants and products, and the expansion of the paste during setting, which is of the order of
1%. (iii) Finally, the resistance reached a relatively constant value at the end of the hydration
process; a further slight increase was due to the drying-out process. The differences in the temperature changes in the two plasters may be due to the rate of dissolution, which does not seem
to depend only on crystallite size and specific surface area but is possibly also related to the
crystal habit and lattice perfection. A crystal habit with more preferential sites for the chemisorption of water would be expected to give a product with a faster dissolution rate.

Fig. 3. SEM pictures of the two forms of hemihydrates.

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61

Table 1
Properties of a- and b-hemihydrates [19]
Properties

Calcium sulphate hemihydrate

a-Hemihydrate

Water of crystallization (wt%)

Density (g/cm3)
Solubility in water at 20  C, g/100 g solution
Refractive indices na, nb, ng
Lattice symmetry
Space group
Lattice spacing (nm) a, b, c

b-Hemihydrate
6.21

2.757
0.67

2.619e2.637
0.88
1.559, 1.5595, 1.584
Rhombohedral
C322 D63
0.683, 0.683, 1.270

The rate of heat evolution and the total heat evolved during the hydration of the two
types of hemihydrates are given in Fig. 6. The rate of heat evolution is faster in the case of
a-hemihydrate. For comparison a-hemihydrate from two different sources was taken and it
was found that they have different rates of heat evolution as well as the total heat evolved.
Thus it is difficult to say unequivocally about the differences in the hydration characteristics
of the two forms (a- and b-) of hemihydrate. The differences may be due to differences in
particle size distribution and or the impurities obtained from different raw materials and not just
by the thermodynamic stability of the materials [28].

Fig. 4. Hydration of a- and b-hemihydrates studied by measuring temperature changes as a function of time (w/p 0.6).

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Fig. 5. Hydration of a- and b-hemihydrates studied by measuring electrical resistance as a function of time (w/p 0.6).

120

80
-HH without additive
70

100

Heat flow [mW/g]

-HH
commercial product

50

80

60

40
-HH
commercial product

30

40

20

Cumulative heat [J/g]

60

20

10

0
0

Time [h]
Fig. 6. Rate of heat evolution and total heat evolved during the hydration of different hemihydrate pastes at 25  C
(unpublished results).

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3. Kinetics and mechanism of hemihydrate hydration

Calcium sulfates constitute a group of inorganic binders that has been utilised by man since
ancient times [29]. The most commonly used reaction in the group is the reaction of calcium
sulphate hemihydrate, CaSO4$0.5H2O, with liquid water to form calcium sulphate dihydrate.
The general form of the reaction kinetics is sigmoidal (Fig. 7) where one can identify three
time regions: an induction period, an acceleratory period and a period involving a very slow
reaction (the completion of hydration).
In order to explain the hydration process a number of kinetic models have been proposed
[30e34] and reviewed by Hand [35]. The most conventional method of describing a sigmoidal
reaction is the Avrami equation which is generally applied for nucleation controlled processes;
a 1  expat m

where a is the fraction of hemihydrate that has been hydrated at a time t. The component m
depends both on the time law for new crystal formation and the growth rate of an individual
crystal. Avrami equation concentrates on nucleation and growth and does not follow the dissolution phase of the reaction. Dissolution is an important feature of any process requiring solution such as the hydration of hemihydrate; thus the Avrami equation is expected to have limited
validity for this system. The other important alternative equations were proposed by Ridge [30]
and Schiller [36]. Both proposed equations based on the geometry of the hemihydrate and dihydrate crystals on the premise that the rates of dissolution of hemihydrate and recrystallisation
of dihydrate are proportional to their respective crystal surface areas. Hand [35] on the basis of
numerical calculations compared the models proposed by Ridge and Schiller and that with the
Avrami equation. It is found that at least for some ranges of data all the three approaches are
compatible and that within the limits of experimental evidence presented so far there is no conclusive evidence which justifies the use of one model rather than the other. However Ridge [37]
did not agree with Hands conclusion. According to Ridge, Hand used Avramis equation to
generate theoretical hydration curves for calcium sulphate hemihydrate, and then has used
data derived from them to test equations due to Ridge and Schiller. But Avramis equation
has no established validity in the field and is, in fact, irrelevant.

Fig. 7. Schematic of the fraction of hemihydrate hydrated as a function of time showing a sigmoidal distribution.

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64

Most of the researchers agree that the hydration of hemihydrate leading to the formation of calcium sulphate dihydrate occurs through a solution mechanism [14,38e42], i.e., the hemihydrate
first dissolves and then the dihydrate precipitates from the aqueous solution because it is less soluble
than the hemihydrate [43]. Thus when hemihydrate is mixed with water, a part of it immediately
dissolves making the solution saturated with respect to Ca2 and SO2
4 ions. This saturated solution
becomes supersaturated with respect to calcium sulphate dihydrate leading to nucleation and crystal growth. In order that crystallization can take place, the nucleating embryo must have a critical
size. The critical radius (rc) is related with the supersaturation (S ) in the following manner [44].
rc

2sy
kTlog S

where s is the surface energy per unit area, y is the molecular volume, k is the Boltzmann
constant and T is the temperature in Kelvin. From Eq. (2), it is obvious that decreasing the
supersaturation decreases the nucleation probability by increasing rc. During the induction
period, clustering of hydrated Ca2 and SO2
4 ions occur, leading to the formation of calcium
sulphate dihydrate nuclei. The nuclei which acquire a certain critical size then start the crystallization of calcium sulphate dihydrate. However, the crystallization process depends on various
factors such as solution saturation/supersaturation, impurities, type of hemihydrate and its
surface area, temperature, water/plaster ratio, etc.
In general, crystals grow by incorporation of growth units into the lattice at a surface. Crystal
surfaces often consist of flat terraces separated by steps. Kink sites occur along these steps and
they are considered to be the most active growth sites. It has been assumed that crystals grow
from aqueous solutions by direct integration of growth units into the lattice at kink sites. As a consequence, monolayer steps advance, which has been experimentally confirmed [45]. Experiments
(not in the hemihydrate system) conducted by Bosbach et al. [45] have shown that gypsum crystals grow by a nucleation and crystal growth mechanism. Gypsum crystal has a layered structure
2
2
consisting of two Ca2/SO2
4 layers parallel to (010) (Fig. 8). Two Ca /SO4 layers, which are
bound together by ionic interactions, form one growth slice parallel to (010). These growth slices
are separated by H2O layers. A perfect cleavage occurs along the H2O layers parallel to (010).
Surface nucleation is a very important process for generating new steps on the (010) surface
at least at high degrees of supersaturation. Equidimensional surface nuclei are formed on the
(010) surface of gypsum, which are most likely surrounded by (001) and (100) steps. After a nucleus has been formed, growth occurs via advancing monolayer steps, predominantly parallel to
(101) and (001). The step velocity of (101) steps is higher, relative to (001) steps, which is a result of a higher step energy for (101) steps.
4. Effect of accelerators on gypsum crystal growth during hemihydrate hydration
In general it has been observed that strong inorganic acids, as well as salts of strong acids
and strong or weak bases are accelerators [46,47]. This type of acceleration has been referred to
as a general ionic strength effect, which is due to the presence of noncomplexing ions [35]. In
addition to this, specific interactions occur since some salts are better accelerators than others.
Accelerators are believed to promote the hydration of hemihydrate to dihydrate by the following two mechanisms [17]:
(i) by increasing the nucleation through a seeding action and

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65

Fig. 8. (a) Atomic structure of a gypsum (010) growth slice, (b) gypsum crystal morphology with forms (010), (120),
(011) and 111 which are commonly observed [45].

(ii) by modifying the rate at which calcium and sulphate ions are transported to, and are
incorporated into the lattice of the growing dihydrate phase through an increased dissolution rate of the hemihydrate.
Lewry and Williamson [2] have studied the effect of a number of sulphate accelerators during the hydration of hemihydrate. Dihydrate, when added to hydrating hemihydrate, accelerates
the hydration. The increased surface area and the amount of dihydrate additions increased the
acceleration of hydration by providing enhanced nucleation sites. However, surface roughness,
i.e., crystal imperfections at dihydrate crystals will also accelerate the hydration.
In the presence of dihydrate as an accelerator, the crystal morphology is changed [2]. The
interlocking needles (15 mm  1 mm  1 mm) for the set or solidified a-hemihydrate became
thinner and shorter. The needles were typically 10 mm  0.5 mm  0.5 mm in the presence of
a 2 wt% addition. This change in morphology gave a significant reduction in intercrystalline
bonding which resulted in decreased strength.

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Ridge et al. [48] studied the accelerating effect of various anions and cations on hemihydrate
hydration and found that K2SO4 is the most effective accelerator. Lewry and Williamson [2]
found that the accelerating effect of K2SO4 increased with up to 2 wt% additions but after
that there was no detectable change. It is believed that K2SO4 accelerates the hydration by increasing the rate of hemihydrate dissolution [18]. According to Chatterji and Kapse [49], the
hemihydrate grains in the paste were covered with an adsorbed layer of water molecules. In
the presence of K2SO4, this layer is stabilized and an orientation of the neighbouring water molecules occurs, resulting into a multilayer dissolution rate.
K2SO4 increased the dihydrate crystal growth in both the [001] directions and in directions
normal to the needle axis. The resulting dihydrate needles were larger, and had a lower aspect
ratio and reduced intercrystalline bonding. Consequently the set paste had a reduced mechanical strength.
The use of an in situ nucleation/acceleration system [2] using KHSO4 and Ca(OH)2, to precipitate microcrystalline dihydrate nuclei in the presence of K2SO4, resulted in a rapid setting
of plaster with smaller reduction in set strength.
5. Effect of retarders on gypsum crystal growth during hemihydrate hydration
Many technologies require crystallization strategies that provide control over the structure,
size and morphology of crystals. Additives of both an organic and inorganic nature play an important role in crystallization processes. They alter the surface properties of the crystals which
lead to changes in nucleation and growth and thereby to changes in the shape of the crystals as
well as in their agglomeration or dispersion behaviour. The growth of calcium sulphate dihydrate is of considerable importance since it is frequently encountered both in nature and industrial processes. Many polymeric additives are used as scale inhibitors in industrial processes to
prevent unwanted CaCO3 and CaSO4 formation in pipes, boilers, heat exchangers and so on.
They are also used as retarders or accelerators to control hydration in the plaster and concrete
industries. The use of retarders during the hydration of hemihydrate to control gypsum crystal
growth is of practical concern. It has in general been observed that weak organic acids and their
salts with strong bases act as retarders [46,47]. Organic colloids that are the decomposition and
hydrolysis products of biopolymers such as proteins as well as salts of phosphoric acid or boric
acid also act as retarders for hemihydrate hydration [19].
Retarding effects of carboxylic acids have generally been studied by measuring temperature
changes or the rate of change of heat evolution or electrical conductance during the hydration of
hemihydrate. Temperature rise during the hydration of a-hemihydrate in the presence of 0.05
wt% carboxylic acids are shown in Fig. 9. From the figure it is clear that when water was added
to a-hemihydrate, hydration started with a rise in temperature. In the case of the reference sample the temperature rise started within 5 min after the addition of water and reached a maximum
value soon. Subsequently the temperature decreased because of heat losses. This temperature
rise is due to heat release during the crystallization of calcium sulphate dihydrate. Since there
is a rapid temperature rise, the crystallization of calcium sulphate dihydrate starts immediately.
In the presence of 0.05 wt% carboxylic acids the curves are similar but with a different induction period and time for maximum rise in temperature. The higher the induction period and the
higher the time for maximum rise in temperature, the higher is the retarding power of the acid.
The retarding sequence is given as:
Citric acidCA > Malic acidMA > Succinic acidSA > Tartaric acidTA

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Ref.
MA

Temperature, C

70

SA
CA

60
50
TA

40
30
20
0

200

400

600

800

1000

1200

Time, min
Fig. 9. Variation of temperature with time during the hydration of a-hemihydrate in the presence of 0.05 wt% carboxylic
acids, (w/p 0.35) [50].

The retardation also increased with increase of acid concentration (Fig. 10).
When a-hemihydrate was added to water, calcium and sulphate ions go into the solution
making the solution saturated or supersaturated with respect to dihydrate. After this gypsum
nuclei of critical size are formed (induction period) and the crystallization starts with the hardening of the hemihydrate. However, in the presence of carboxylic acids, the gypsum crystallization and hardening processes are delayed. It is reported that the carboxylic acids are
chemisorbed at the surface of growing gypsum nuclei during the induction period delaying
the crystallization and hardening processes. This suggests that in the presence of carboxylic
acids the normal growth kinetics is changed. The degree of change will depend on the extent
of chemisorption and its rate. These two processes will, however, depend on the method of
preparation of the hemihydrate, its surface area and surface topography, affinity of carboxylic
acid molecules towards the surface of gypsum crystals, molecular configuration and concentration of acids, etc. Adsorption (chemisorption) of carboxylic acids on the surface of pure calcium sulphate dihydrate has been confirmed by DSC and FTIR techniques [14].
Badens et al. [4] studied the effect of adipic, tartaric, malic and citric acids on the hydration
of b-hemihydrate by measuring the electrical conductivities of the suspension. The typical conductivity curves are shown in Fig. 11. The additives were introduced into the solution prior to
the calcium sulphate hemihydrate. The three different stages, observed in Fig. 11, correspond to
the hemihydrate dissolution, the gypsum nucleation and the gypsum growth. The first plateau
corresponds to the apparent saturation concentration of calcium hemihydrate and the second

Ref.

Temperature, C

70

0.05

0.15

0.10

0.20
0.25

60
50
40
30
20
0

500

1000

1500

2000

Time, min
Fig. 10. Variation of temperature with time during the hydration of a-hemihydrate in the presence of different concentrations (wt%) of malic acids (w/p 0.35) [50].

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Fig. 11. Variation of electrical conductivity versus time for the hydration of b-hemihydrate suspension (50 g L1 at
20  C) in the presence of different acids (concentration 1000 ppm) [4].

plateau to the saturation concentration of gypsum. In the case of adipic and meso-tartaric acid at
1000 ppm the conductivity measurements do not show any difference with pure solution,
whereas the rate retarding effects of citric and D,L-malic acids are clearly shown. It was found
that acids were adsorbed on gypsum crystals. The higher the initial concentration of the acid,
the higher the adsorption on gypsum crystals (Fig. 12).
Further in order to confirm the adsorption of carboxylic acids on gypsum crystal surfaces,
Badens et al. [4] tried to explain their results in terms of charge density and structural matching
between the active sites of the molecule of carboxylic acids and adsorption sites on the crystals
of gypsum. The (120) and 111 faces of gypsum crystals were found to be involved in adsorption. In fact the interaction between the carboxylic acid molecules and the gypsum crystal faces
should be electrostatic in nature because of the ionization of the acids. The higher the anionic

Fig. 12. Influence of D,L-malic acid concentration on the extent of adsorption for different time intervals [4].

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charge density, the higher should be the interaction. Citric acid has three ionisable carboxylic
groups, i.e. that can give rise to the highest anionic charge density. Also the distance between
two of the oxygen ions of the two carboxylic group of the molecule of citric acid is exactly the
) as the distance between two neighbouring calcium ions on the gypsum crystal
same (4.0 A
faces ((120) and 111). Thus the adsorption of citric acid on the surface of a gypsum crystal
can be maximum, resulting in a maximum retardation of hemihydrate hydration.
The D,L-malic, meso-tartaric and adipic acids have the same anionic charge density but their
structural matchings are different. The meso-tartaric acid shows a better matching than the D,Lmalic acid but, the hydroxyl group of the molecule of meso-tartaric acid probably induces steric
hindrance and consequently the D,L-malic acid is a better inhibitor of gypsum crystallization
than meso-tartaric acid. Adipic acid does not have any inhibitor effect.
The distance between the two oxygen ions of the active sites is much more important than
the distance of two first neighbours of calcium ions on the gypsum crystal.
Hill and Plank [51] studied the growth of gypsum crystals in the presence of tartaric and citric
acids using molecular modeling and calculated the surface energies of gypsum and hemihydrate
crystal faces. It was found that at high pH tartaric acid inhibits both the growth of gypsum and the
dissolution of hemihydrate, while at low pH, both the acids inhibit the growth of gypsum.
The effect of Retardan P, a commercial retarder (some derivative of g-amino butyric acid
formaldehyde condensate) on the hydration of b-hemihydrate has been studied. The rate of
heat evolution depends on its concentration (Fig. 13). The higher is the concentration, the longer is the induction period and the time for maximum heat evolution.
Boisvert et al. [52] studied the retarding influence of sodium poly(acrylate) (PANa) on the
hydration of hemihydrate to investigate hemihydrate dissolution on homogeneous and heterogeneous gypsum nucleation and crystal growth. It is found that in spite of the relative affinity
of PANa for the hemihydrate surface, adsorption of the PANa onto the hemihydrate surface
14
Reference

12

Rate of heat evolution [J/g/h]

Retardan P 0.01%
Retardan P 0.02%

10

Retardan P 0.03%
Retardan P 0.05%

0
0

20

40

60

80

Time of hydration [h]

Fig. 13. Effect of different concentrations of Retardan P on the rate of heat evolution during the hydration of
b-hemihydrate at 25  C (unpublished results).

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does not hinder its dissolution even with a high surface density. However, adsorption on gypsum
nuclei can slow down gypsum growth but cannot stop it. The results showed that as soon as a stable gypsum nucleus is formed, hemihydrate hydration will proceed to its end and all the hemihydrate will become gypsum. Once gypsum is present, the rate of the hydration can be slowed
down but the process cannot be stopped. The only way that PANa can prevent hemihydrate hydration is by blocking the nucleation of gypsum. The authors have concluded that heterogeneous
nucleation is the key process that controls hydration of a system in which hemihydrate dissolution, gypsum nucleation and growth are all occurring at the same time in a continuous manner.
6. Gypsum crystal morphologies during hemihydrate hydration
In general during the hydration of hemihydrates, needle shaped gypsum crystals with a high
degree of interlocking are formed and additives modify the morphology and habit of growing
gypsum crystals resulting in microstructures involving changes in capillary porosity and mechanical properties. Retarders are generally adsorbed on the steps and kinks of gypsum crystal
faces which results in changes of morphology. Scanning electron microscopic images of a- and
b-hemihydrate hydrated for 28 days in the absence and presence of different carboxylic acids
(0.2 wt%) are shown in Fig. 14. In the absence of acids in both the cases gypsum crystals with
a high degree of interlocking can be seen. The carboxylic acids, except tartaric acid, modify the
morphology of calcium sulphate dihydrate crystals in almost a similar way in both the hemihydrates. It has already been reported that tartaric acid acts as retarder only in the presence
of calcium hydroxide [1]. From the figure it is obvious that the crystal morphologies are functions of the nature and concentration of the additives. From microstructural observations one
can predict that the retarders will reduce the strength of the hardened gypsum plaster.
In general in any crystallization process from solution, nuclei formation controls the overall
kinetics of crystal growth which in turn controls the morphology and microstructures of the material. It appears that the additives modify the process of nucleation by changing the solution
saturation/supersaturation and the surface topography of the growing crystals. Imperfections
on different surfaces of growing gypsum crystals may also change. These changes may depend
on the nature, molecular configuration, molecular weight and the concentration of the additives.
Since different additives have different molecular configurations and properties, they affect the
process of nucleation and crystal growth in different ways leading to the development of different microstructures. It may be possible to have a correlation between the type of additive
and the microstructural developments provided detailed investigations are made.
In the past, many attempts have been made to correlate the morphological developments of
crystals with their crystal structure. During their growth crystals adopt a variety of habits due to
differences in relative growth rates of faces of which the crystal is composed. Correlations
between evolution of various crystal faces during crystal growth, their relative growth rates
and the crystallographic structures of crystals, have recently been discussed and reviewed by
Prywer [53]. Theoretically, a bulk crystal may possess an infinite number of faces but real crystals possess a limited number of faces, particularly those which grow most slowly. According to
Wulffs theorem [54] the equilibrium form of a crystal would be such as to minimize the total
surface energy for a given volume. Thus, the crystal would be bounded by faces located at distances proportional to their surface energies. The largest faces are expected to be the faces with
the lowest surface energies. Such faces are also those with the greatest interplanar distances
dhkl. The interplanar distance dhkl is the distance that separates physically identical surfaces.
According to the BravaiseFriedel law [55,56], the observed crystal faces are those with the

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Fig. 14. Effect of 0.2 wt% carboxylic acids on the microstructure obtained from hemihydrates hydrated for 28 days.

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largest interplanar distances. The larger the interplanar distance, the more morphologically
important is the corresponding crystal face. Morphological importance (MI) of a given face is
defined as its relative size in a given crystal morphology. Later, it was shown, first by Niggli
[57] and then by Donnay and Harker [58] that this law is sometimes violated. Donnay and
Harker extended this law by considering the screw axis and the glide planes, i.e., the symmetry
elements due to space group symmetry. In general MI is inversely proportional to the relative
growth rates of faces. This is not always true because even a small fluctuation in growth conditions can induce big changes in relative growth rates, which may lead to the fast disappearance of a given face from crystal morphology.
Seed crystals enhance the crystallization rates and apart from changing the crystal growth
rate, also modify the crystal morphology. If the growth morphologies originating from two
different seeds are compared, the biggest differences in crystal morphologies appear when
the differences in interfacial angles are big. From this it follows that the geometry of the
seed and, generally, crystal geometry plays a key role in the formation of crystal habit. The
influence of seed-faces on the growth morphology also depends on the growth time.
7. Mechanical properties of the hardened gypsum plaster
Measurements of the E-modulus of elasticity, compressive strength and total porosity values
of a-hemihydrate hydrated for 28 days in the presence of different concentration of carboxylic
acids (Figs. 15e17) show that there is no regular change in the values with the acids and their
concentrations [50]. Strengths in general were found to be maximum in the absence of any
additive. The compressive strength and the total porosity variations with acids and their
concentrations follow the same sequence. The effect of different concentrations of citric acid
on the E-modulus and compressive strengths in the case of b-hemihydrate hydrated for 28
days are also shown in Fig. 18. With a decrease of the water/plaster ratio both the E-modulus

E-Modulus [N/mm2]

20000

18000

16000

0.

15

0
SA

25
0.

0.
2
SA

15
SA

0.

0
TA

25

0.
2
TA

0.

15
0.
A

TA

20
0.
M

25
M

0.

0.
A
C

M
A

10

15
0.

20
C

0.

0.
2
A

ef

er

en

ce

14000

Fig. 15. Effect of different concentrations of carboxylic acids on the E-modulus of a-hemihydrate hydrated for 28 days.

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60

Compressive strength [N/mm2]

50

40

30

20

10

SA

0.

0.
15

20

25
SA

SA

0.

0.
15

20

TA

0.
TA

TA

0.

25

0.
15
M

0.
A
M

20

25
0.

0.
10

A
C

0.
15

20
0.
A

ef

er

0.

en

25

ce

Fig. 16. Effect of different concentrations of carboxylic acids on the compressive strength of a-hemihydrate hydrated
for 28 days.

and the compressive strength increase, but there is a sudden decrease in the values after a certain
concentration of the acid.
Morphological studies have shown that the strength developments in the hydrating hemihydrate paste are related to the interlocking structure, size, shape and macro defects of gypsum
35

30

20

15

10

15
0.

20

Fig. 17. Effect of different concentrations of carboxylic acids on the total porosity.

SA

0.
SA

25
0.
SA

0.

15

20
TA

0.
TA

25
0.
TA

0.
A
M

M
A

0.

15

20

25
0.
M

0.
C
A

0.
A
C

10

15

20
C

0.

0.
A
C

ef

er
e

nc

25

Total Porosity [%]

25

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53 (2007) 57e77

Fig. 18. Effect of different concentrations of citric acid on (a) the E-modulus and (b) the compressive strengths in the
case of b-hemihydrate hydrated for 28 days.

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crystals. Finot et al. [59] with the help of atomic force microscopic studies proposed that the mechanical properties, besides interlocking structures, are also due to forces of adhesion between
gypsum crystals during the setting and these forces are higher in magnitude than van der Waals
forces. Mathieu and Boistelle [60] also proposed that the mechanical strength of the set plaster is
due to an interlocking structure and intercrystalline interactions. As the crystal morphology
changes, the faces of the crystals involved in the interaction also change. Different carboxylic
acids modify the morphology of gypsum crystals to different extents. Carboxylic acids have
different molecular structure, functional groups, acidic character, affinity for adsorption on
growing gypsum crystals, etc. and hence they will affect the force of adhesion between different
faces of gypsum crystals to different extents. Thus it is the combined effect of the interlocking
structure and the force of adhesion between gypsum crystal faces, which control the mechanical
properties.
8. Summary
Hydration reactions of both a- and b-hemihydrates are highly exothermic in nature and proceed by closely related routes, but with some differences. The differences are due to the
methods of preparation, specific surface area, crystal size and habit, imperfections and surface
topography. Hydration reactions are nucleation controlled processes which result in the growth
of gypsum crystals. In pastes interlocking structures are obtained which are responsible for their
strength. However, in the presence of additives the nucleation and the crystal growth processes
are changed and the resulting change of microstructures decreases their physico-mechanical
properties. In the presence of retarders (carboxylic acids), it is inferred that the acids are adsorbed at the crystal surfaces of the growing gypsum thereby modifying the overall processes.
In the presence of additives the interlocking microstructures can be lost resulting in a decrease
of their strength. In addition to this the force of adhesion between gypsum crystals also controls
the mechanical properties.
In order to fully understand the process of gypsum crystallization by hemihydrate hydration,
it is necessary to carry out studies of the growth kinetics using seed crystals having a range of
different properties. These should include seeds of different dimensions and crystallographic
morphology. It is important to understand the role of the size and stability of critical nuclei
as well as that of the different crystal faces and step edges of gypsum. Here the interaction
with additives at the molecular level as well as the forces between crystals can be crucial in
determining the ultimate properties of the final product. In essence the future requires studies
of gypsum crystallization from a nanoscale perspective.
Acknowledgments
Part of the work was done at University of Kassel and authors are thankful to Prof. Michael
Schmidt for providing necessary laboratory facilities. Prof. N.B. Singh (DDU Gorakhpur University, India), thanks Alexander von Humboldt foundation for awarding a fellowship under resumption of fellowship programme.
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