Construction and Building Materials 149 (2017) 535–542

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Study of modified gypsum binder

Nataliia Kondratieva a,⇑, Maud Barre b, François Goutenoire b, Myroslav Sanytsky c
a
Ukrainian State University of Chemical Technology (USUCT), Department Chemical Technology of Binding Material, av. Gagarina 8, 49005 Dnipro, Ukraine
b
Institut des Molécules et Matériaux du Mans IMMM, UMR CNRS 6283, LUNAM, Université du Maine, 72085 Le Mans Cedex 9, France
c
Lviv Polytechnic National University, S. Bandera Str. 12, 79013 Lviv, Ukraine

h i g h l i g h t s

Kinds of additive have influence on the hydration process and the gypsum structure.

The additive content enhances the compressive strength and water resistance of gypsum.

With additives a denser finecrystalline structure is formed.

Taurit and silica introduced together increase the durability characteristics.

a r t i c l e i n f o a b s t r a c t

Article history: Nowadays the addition of small amounts of chemical additives allows developing new types of binding
Received 1 March 2017 materials. The effect of microadditives on the performance of b-hemihydrate gypsum has been studied.
Received in revised form 11 May 2017 1% content of complex additive contributes to enhancement of compressive strength and water resis-
Accepted 15 May 2017
tance in modified samples as compared to reference one. These studies showed that additives accelerate
the rate of hydration and lead to the formation of a dense and well-compacted texture of crystals, thereby
imparting, to gypsum matrix, higher strength and better water resistance than the reference materials.
Keywords:
Ó 2017 Elsevier Ltd. All rights reserved.
Gypsum
Additive
Hydration
Microstructure
Hydration products

1. Introduction The properties of materials depend on their compositions and

The range of application of gypsum building materials and
products is significantly inferior to the similar materials based on
cement because of their low strength and water resistance. Basi-
cally, gypsum materials and products are used indoor in dry and
normal humidity conditions.
One of the most effective ways to increase gypsum’s water
resistance and strength is using different additives. Researches
are carried out in several directions, among which is the investiga-
tion of the processes of structure formation under the influence of
various factors, plasticizers of different actions, additives etc [1–3].
The aim of the investigation is to establish the influence of addi-
tives of modifiers on the structure and properties of gypsum bin-
ders, studying the process of structure formation of gypsum
hydration systems.
⇑ Corresponding author.
E-mail address: Nataliyavk@yahoo.com (N. Kondratieva).
structures that are interconnected and in balance. Creation of
materials with special properties should be based on the main
knowledge of the material’s structure: laws ruling its formation
and regulation of its properties influencing the structure as part
of the process. A key element of the triangle structure-property-
technology is the concept of structure that is closely related not
only to important properties of material but also to the conditions
of technological processes.
That is impossible without solving the problem of theoretical
generalization and further study of the complex processes that
lead to the formation of structure, to physic and mechanical
properties of binding materials and their connection with the
composition of the starting materials. Most of the works in the
field of gypsum binders were devoted to the study of processes
from a physical-chemical mechanics point of view [2,4–8].
However, these studies do not reveal the relationship between
the structure of the crystal lattice of gypsum binders and their
reactivity. In other articles, influence of pH, temperature and
additives concentration on crystallographic variety and structure

http://dx.doi.org/10.1016/j.conbuildmat.2017.05.140
0950-0618/Ó 2017 Elsevier Ltd. All rights reserved.
536 N. Kondratieva et al. / Construction and Building Materials 149 (2017) 535–542
of gypsum were reported without mechanical properties observa-
tion [9–12].
The action of modifiers appears through the processes in the
interfaces of solid, liquid and gaseous phases. Adsorption layers
of modifiers on the surface of the solid particles have different
important tasks: influence on rate of crystal growing, its
morphology and crystallographic varieties.
One of the main difficulties is that the modified systems are
multicomponent. Then, the individual and joint influences of com-
ponents should be taken into account, but are difficult to represent
in an analytical form.
The results of researches show differences that are related to
the concentration of additives and to properties modifications.
The content of modifiers is significantly different in many works
(within 0.025–0.15%). The reported rates of strength increase are
from 20 to 50%. Differences between the results and absence of
clear dependences can be explained by the following factors: kind
of additive, synthesis parameters, structural and morphological
features, method of addition into binder and degree of dispersion
of modifiers, on one hand, and chemical composition of the surface
of the binder, on the other hand [13].
Some of the most common hypotheses which explain the
change in the properties of gypsum binder with micro- and
nanoadditives can be enumerated [14–17]:
– nanoparticles change the surface charge and then affect electro-
conduction properties;
– rheological properties are modified;
– nanostructures act as crystallization centers;
– high density of contact points increases the traction between
particles:
– nanoparticles introduction is connected with active surface area
and the surface energy excess that influences the crystal
morphology.
The algorithm to solve the problem of rational modification can
be represented as follows:
– study of wide range of modifiers to identify positive impact;
– definition of technological methods for addition of small quan-
tity of modifiers;
– study of the structural and morphological changes in the hydra-
tion products;
– definition of features of structure formation with different
modifiers.
Structures of gypsum binder formed with various additives
were investigated in this research work.
2. Experimental section
2.1. Instrumentation
The phase compositions of the resulting products were determined by X-ray
powder diffraction: patterns were recorded at room temperature with Cu Ka radi-
ation on a PANalytical X’pert Pro diffractometer equipped with the X’celerator
detector in the 2h range from 5° to 70° (step 0.033°, time/step 50 s). To prepare
the samples the powder was sieved with 63 lm mesh. The phase identifications
and Rietveld refinements were performed with X’Pert HighScore Plus software. In
our samples, the diagrams’ analyses led to the identification of several phases which
are gathered with their structural data in Table 1. These structural data were down-
loaded as files in the format ⁄.cif and used to perform Rietveld refinement and
phase quantification.
Thermal analyses were carried out by using Q600 SDT TA Instruments equip-
ment. The temperature was raised from RT up to 800 °C at a heating rate of
10 °C/min under dry air flow (100 mLmin1) with a-Al2O3 as reference.
Changes in the microstructure of composites were observed by SEM. SEM
images were carried out on a JEOL, JSM 6510 LV microscope working with W fila-
ment and an accelerating voltage of 15 kV.
2.2. Materials
Composites based on gypsum binder have been investigated in this research.
The basic component of composite is gypsum plaster G-4-H-IIc, which was made
in ‘‘Kamenetsk-Podilsk” (Ukraine).
The X-ray characterization shows that gypsum plaster G-4 contains 66.5% of
CaSO40.5H2O, 17.0% of CaSO4, 12.0% of CaSO42H2O, traces of SiO2 and CaCO3
(Fig. 1, Table 1).
Taurit TS-D and white druss (silica) were used as additives to gypsum
composite.
The density of Taurit TS-D is 493 kg/m3. Taurit brand ‘‘TC-D” (Kazakhstan) is
used as a stable color pigment in the manufacture of different kinds of building
materials. Taurit brand ‘‘TC-D” has following features: increases frost resistance;
shine and volume-lasting color, from gray to dark-gray color; accelerates time of
setting; increases the water resistance of products; gives an excellent surface
appearance; increases durability, initial and final strength of binder [18]. The
corresponding X-ray diffraction diagram and its identification are given in Fig. 2.
White druss (silica) is a commercial product (Ukraine). It contains SiO2 and its
particles have average size 50–77 nm. Silica is used as a fine-grained filler for com-
posite material. According to results of X-ray diffractometry, silica is amorphous.
2.3. Preparation of test samples
Different compositions of samples were prepared in order to investigate the
effect of additives.
At first, the main properties of gypsum without additive were investigated
according to the National Standard of Ukraine DSTU < B.2.7-82: 2010 Building materi-
als. Gypsum binders. Homogeneous paste of gypsum was prepared manually by
admixing hemihydrate gypsum G-4 with water. The quantity of water required to
produce paste of standard consistency was 50 wt% and was determined in previous
tests for this kind of gypsum plaster. The measured compressive strength of sam-
ples is 4.2 MPa.
For samples with additives, Taurit and silica were added to hemihydrate gyp-
sum plaster G-4 and thoroughly mixed, after that, water was added to get paste
of standard consistency. Mixed compositions of gypsum plaster with different addi-
tives are presented in the Table 2.
Immediately after mixing with water, the samples were casted into metal
molds of size 40  40  160 mm. After 2 h, the samples were unmolded and tested
for compressive and flexural strength. Six samples from different compositions
were used for each test.
Water resistance coefficient was defined as a ratio of compressive strength in
water-saturated state to compressive strength in dry state.
3. Results and discussion
3.1. Preparation and physical properties measurements
At the first stage of the research, gypsum paste of normal con-
sistency and standard specimens were tested. The following
parameters were investigated: time of setting of gypsum paste
(s); compressive (Rc) and flexural strength (Rf) of gypsum speci-
mens; water resistance coefficient (kw).
In order to investigate the influence of additives on gypsum bin-
der, different compositions of samples were prepared by adding
Taurit and silica, in the weight range from 0.5 to 1.0%, to gypsum
plaster. As the reference material, hemihydrate gypsum G-4 with-
out additive was used. The optimal concentrations of additives
were found: Taurit – 1.0%, silica – 1.0%, complex additive: Taurit
0.5% and silica 0.5%, which were added to gypsum hemihydrate
over 100%.
3.2. Hydration process
Hydration of hemihydrate gypsum is an exothermic reaction
and occurs as:
CaSO4  0:5H2 O þ 1:5H2 O ! CaSO4  2H2 O þ Q
In order to compare the hydration activity of gypsum binder
with different additives, the temperature variation of the paste
(water-gypsum ratio is 0.5) was measured as a function of time.
The study of the temperature of the hydration process showed
that addition of modifiers to gypsum binder holds to an intensifica-
tion of the hydration process. The curve of temperature’s increase
 N. Kondratieva et al. / Construction and Building Materials 149 (2017) 535–542 537

Table 1
Structural data of the different phases quantified by X-ray diffraction.

Title Space group Cell a [Å] Cell b [Å] Cell c [Å] Cell alpha [°] Cell beta [°] Cell gamma [°] Density
Gypsum CaSO4 2H2O C 1 2/c 1 6.2886 15.1929 5.6823 90 114.21 90 2.26
Bassanite CaSO4 0.5H2O P 31 2 1 6.9348 6.9348 6.3359 90 90 120 2.72
Anhydrite CaSO4 Cmcm 6.9919 6.2372 6.9931 90 90 90 2.96
SiO2 P 31 2 1 4.9545 4.9545 5.2699 90 90 120 2.67
Calcite CaCO3 R -3 c 4.9786 4.9786 17.0144 90 90 120 2.73

Fig. 1. Rietveld refinement of X-ray powder diffraction diagram of gypsum plaster G-4.

Fig. 2. Phase identification from X-ray powder diffraction of Taurit.

presents 3 sections: an induction period, an acceleration period 3.3. Thermal analyses

and a period involving a very slow reaction (the completion of
hydration). The hydration reaction for samples with additives
(Fig. 3) begins earlier (the induction period is shorter) and is more
intensive; the time to reach the maximum hydration temperature
is shorter (11 min) than for gypsum without additives (16 min).
During hydration, gypsum crystallization takes place. When
the hydration occurs in pastes, the plaster sets and develops
strength.
On the thermograms (Fig. 4) of the specimens we can see the
endothermic peak, in the temperature range 145–150 °C, responsi-
ble for the evaporation of crystallization water.
CaSO4  2H2 O ! CaSO4  0:5H2 O þ 1:5H2 O
Exothermic peak at 360–370 °C is attributed to the reconstruc-
tion of crystalline grid of the anhydrite.
538 N. Kondratieva et al. / Construction and Building Materials 149 (2017) 535–542

Table 2
Compositions of samples and their properties.

Concentrations of gypsum hemihydrate Concentrations Compressive strength (Rc), MPa Flexural strength (Rf), MPa Water resistance coefficient
of additives,%
(over 100%)
Taurit Silica
1 100% – – 4.2 2.4 0.33
2 100% 1.0 – 5.9 3.6 0.37
3 100% – 1.0 6.0 4.0 0.42
4 100% 0.5 0.5 7.8 4.2 0.59
5 100% 1.0 1.0 5.4 3.5 0.45
6 100% 2.0 – 4.5 2.5 0.34

Fig. 3. Temperature of the hydration processes of hemihydrate gypsum without additive (1), with Taurit (2), with silica (3) and with complex Taurit and silica additives (4).

Fig. 4. Results of DTA-TG gypsum binder without additives (a) with Taurit (b), with silica (c) and with Taurit and silica complex additives (d).
 N. Kondratieva et al. / Construction and Building Materials 149 (2017) 535–542
2CaSO4  0:5H2 O ! 2CaSO4 þ H2 O
Endothermic peak at 600–700 °C corresponds to the beginning
of the particular calcium sulfate decomposition
2CaSO4 ! 2CaO þ 2SO2 þ O2
We must note that the results of DTA TG for all samples are
similar.
3.4. XRD analyses
The main reflections on the X-ray diffraction patterns recorded
on all the samples (Fig. 5) correspond to the lines of calcium sulfate
dihydrate, but there are differences between modified and non-
modified samples (Figs. 5–9).
The results of X-ray powder diffraction of gypsum with and
without additive show that all samples almost present nearly the
same composition: CaSO42H2O (89.4–92.3%), CaSO40.5H2O (0.8–
2.5%), CaSO4 (0.8–1.3%), traces of SiO2 and CaCO3.
However, X-ray investigation of samples with additives shows
differences in the products of hydration processes. First of all, there
is a difference between the intensities of gypsum main peaks (x) in
the Figs. 6–9 that demonstrates the changes of hydration process
conditions.
Adding Taurit (Fig. 7) decreases the intensities of peaks
d = 0.756, 0.379 nm while the intensity of peaks d = 0.286 nm
(CaSO42H2O) increases. The samples with Taurit contain less
CaSO42H2O than the samples without additives, 2.5% CaSO40.5H2-
O and 1.0% CaSO4 didn’t take part in the reaction of hydration.
A similar phenomenon is observed in the X-ray powder diffrac-
tion (Fig. 8) of gypsum with silica. The intensities of peaks
d = 0.757 (CaSO42H2O) and d = 0.378; 0.305 nm (CaSO4) decrease
while the intensities of peaks d = 0.286; 0.267 (CaSO42H2O)
increase. Peak d = 0.348 (CaSO40.5H2O) nearly disappeared. A little
bit more (1.7%) CaSO40.5H2O and (1.1%) CaSO4 did not hydrate.
In a same way, when Taurit and silica are added separately,
some of the intensities of reflections corresponding to calcium sul-
fate dihydrate slightly decreases and global quantity of unreacted
CaSO40.5H2O and CaSO4 remains unchanged. However, when
complex Taurit and silica additive is added together, the intensities
increase (Fig. 9) and the quantity of gypsum CaSO42H2O is maxi-
mum (92.3%). It means that the reaction of hydration was more
complete.
According to the results of differential thermal and X-ray
analyses of modified gypsum samples, as expected, no new phase
was observed, the amount of additives being not sufficient for
the formation of new phases. Nevertheless, the intensity (Fig. 3)
and the degree (Figs. 5–9) of hydration process are different.
Fig. 5. X-ray powder diffraction diagrams of gypsum without additive (1), with silica (2), with Taurit (3), with Taurit and silica complex additive (4).
539
Thus, the introduction of additives results in better conditions
for hydration followed by more extensive transformation of cal-
cium sulfate hemihydrate into calcium sulfate dihydrate providing
the improvement of crystal structure and mechanical properties of
the gypsum matrix.
3.5. Microstructure analyses
The microstructure analysis of gypsum samples without addi-
tive demonstrates (Fig. 10) that gypsum’s crystals are not ordered
and nonhomogeneous. They are chaotically distributed in the
matrix volume. There are a lot of lamellar crystals, a few numbers
of thin prismatic, which are up to 5 lm long and up to 1–2 lm in
diameter and randomly spread in the matrix volume. Some of crys-
tals have not grown and their form is not developed. Size of such
shapeless individual crystals is 2–3 lm. In this case, a structure
with elevated porosity that results in decreased mechanical dura-
bility of the samples is formed.
SEM micrographs of modified gypsum show that the addition of
Taurit (Fig. 11) influences morphology of mineral units and aggre-
gates. Thus, using modifiers allows creating more compact struc-
ture of gypsum. The shapes of crystals are not mainly lamellar,
there are a lot of thin crystals with columnar formations, but they
are not long and present form of crystal-jams and druses.
With silica (Fig. 12), the conditions for the formation of pris-
matic crystal structures were created. Investigating certain aggre-
gates, it can be observed at Fig. 12 that most of crystals have
prismatic shape, they are longer than crystals with Taurit and some
of them grow together. Porosity of gypsum samples with silica
decreases, thus, the strength of gypsum increases.
The presence of different gypsum crystals shapes indicates that
crystallization of hydrates occurs in specific conditions. An irregu-
lar zone of supersaturation of formative phases and an uneven sur-
face energy lead to the formation of primary crystals of different
shapes. The rate of nucleation and coarsening of crystals in these
samples is irregular.
The microstructural analysis of the samples with Taurit and sil-
ica complex additive demonstrates (Fig. 13) that prismatic crystals,
up to 7–10 lm long and up to 1–2 lm in diameter, spread in the
matrix volume, prevail in the structure of gypsum samples. The
ordered and homogeneous structure with larger crystals (if com-
pared with crystal without additives) is formed in the gypsum
matrix.
Besides, on the picture of the sample with complex additive
(Fig. 13) we can see the packed block structure. Probably, the addi-
tives attract crystals due to high surface energy forming denser
structures. Taurit and silica have high surface energy and play
the role of crystallization centers with the intensive crystallization
540 N. Kondratieva et al. / Construction and Building Materials 149 (2017) 535–542

Fig. 6. Rietveld analysis of X-ray powder diffraction diagram of gypsum without additive.

Fig. 7. Rietveld analysis of X-ray powder diffraction diagram of gypsum with Taurit.

Fig. 8. Rietveld analysis of X-ray powder diffraction diagram of gypsum with silica.
 N. Kondratieva et al. / Construction and Building Materials 149 (2017) 535–542 541

Fig. 9. Rietveld analysis of X-ray powder diffraction diagram of gypsum with complex Taurit and silica additive.

Fig. 10. Microstructure of gypsum’s samples without additive. Fig. 12. Microstructure of gypsum’s samples with silica.

Fig. 13. Microstructure of gypsum’s samples with Taurit and silica complex
Fig. 11. Microstructure of gypsum’s samples with Taurit. additive.
542 N. Kondratieva et al. / Construction and Building Materials 149 (2017) 535–542
of new-formations along their surfaces. These additives possess a
high chemical activity and have a stronger influence on the forma-
tion of the structure of boundary layers of mineral matrix. With the
combined additions, the ordered defectless structure with densely
packed crystalline hydrates is formed. It contributes to the inter-
face area increase, porosity decrease, formation of stronger con-
tacts and improvement of physical and mechanical characteristics.
4. Conclusions
In this paper, it is shown that the kind of additives and their
quantity have influence on the hydration process and the gypsum
structure. The intensity of hydration process increases with
presence of additives. An incoherent and irregular structure con-
sisting in crystals of different morphologies and sizes is formed
in the samples without additive. It results in considerable porosity,
in decreasing the interface contacts and degradation of physical
and mechanical characteristics. When the ultradispersed additive
is added, a denser finecrystalline structure is formed. It increases
the contact area between the crystalline new-formations and then
results in the improvement of the durability of gypsum matrix.
Thus, the formation of finecrystalline structure of gypsum matrix
with optimal additive concentration of 1% provides the growth of
mechanical indexes. If the Taurit and silica additives are intro-
duced together, greater growth of durability characteristics with
the formation of denser structure are achieved in comparison with
the sample containing only one kind of additive. Therefore using
the additives allows obtaining gypsum with fine structure related
to increased strength and water-resistance.
Acknowledgement
The authors express their sincere thanks to Yohann BLIN, Tech-
nician of Faculty of Science, University du Maine for his assistance
with SEM.
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