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High temperature properties of MDF composite based on calcium aluminate

cement and polyvinyl alcohol

Article in Journal of Thermal Analysis and Calorimetry · February 2014

DOI: 10.1007/s10973-013-3481-9

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J Therm Anal Calorim (2014) 115:1245–1252
DOI 10.1007/s10973-013-3481-9
High temperature properties of MDF composite based on calcium
aluminate cement and polyvinyl alcohol
František Šoukal • Petr Ptáček • Jiřı́ Másilko •
Tomáš Opravil • Jaromı́r Havlica • Martina Drdlová
Received: 1 August 2013 / Accepted: 9 October 2013 / Published online: 12 November 2013
 Akadémiai Kiadó, Budapest, Hungary 2013
Abstract The macro-defect-free composites belong to
the well-known group of promising materials consisting of
inorganic binder and organic polymer. MDF composites
exhibit unusual mechanical properties, especially the flex-
ural strength that can reach over 200 MPa. Moreover, the
MDF composites based on calcium aluminate cement have
a good temperature resistance because of the Al2O3 content
in the cement. This paper deals with the preparation and
high temperature characterization of MDF composite based
on calcium aluminate cement combined with polyvinyl
alcohol that could enable its utilization as a refractory
material in industrial kilns. The composition of the MDF
mixture has been optimized for an easy high-shear pro-
cessing and flexural strength of the resulting 7-days cured
material has been studied under laboratory condition and
after heating at 240, 300, 600, 1,000, and 1,500 C. The
structure changes during the heating have been observed by
SEM and the course of processes during the heating has
been investigated by TG–DTA–EGA, TMA and heating
microscopy.
Keywords Macro-defect-free  Composite  High
temperature  Properties  Thermal analysis
F. Šoukal (&)  P. Ptáček  J. Másilko  T. Opravil  J. Havlica
Materials Research Centre, Faculty of Chemistry, Brno
University of Technology, Purkyňova 464/118, 61200 Brno,
Czech Republic
e-mail: soukal@fch.vutbr.cz
M. Drdlová
Research Institute of Building Materials, Hněvkovského 65,
Brno 61700, Czech Republic
Introduction
The Macro-Defect-Free (MDF) composite is a hardened
binder material resulting from hydration of a mixture of
inorganic cement, organic water soluble polymer with low
mixing water content [1]. The properly processed MDF
composites exhibit extraordinary mechanical properties
compared to the conventional cement pastes. Therefore,
MDF composites have been the subject of many investi-
gations and reviews in the last decades. Despite the good
properties, the commercial potential is very limited. The
main factor limiting the use of MDF composites in civil
construction is the deterioration of its mechanical proper-
ties when the material is exposed to humidity [2–5].
Despite many investigations devoted to MDF materials
focused on improving the moisture resistance [6–17], there
are still few suitable application fields found for MDF
composites sheltered from moisture influence; one of them
is a high temperature application as refractory materials.
Therefore, MDF composites made from calcium aluminate
cement can be potentially used in some special refractory
applications.
The refractory materials used nowadays can be classified
into two types according their application way—the shaped
refractories usually hardened by ceramic bond made by
sintering and the unshaped refractories (powder matter)
based on organic and/or inorganic bond used mainly for
monolithic bricking and repairs. The shaped refractory
materials are produced by ceramic technologies using heat
treatment up to sintering. The firing process is high energy
demanding one and usually connected with production of
green house gases caused by combustion of fossil fuels, e.g.,
natural gas. Before the firing, the material has to be shaped to
the required shape by one of the several available technol-
ogies—pressing, casting, injection molding, or extrusion.
123
1246 F. Šoukal et al.

Whereas the unshaped materials are formed at the installa- Premixing

tion site just after the mixing with setting component (usually
water) and the obtained shape is held by an organic and/or 200 g of calcium aluminate cement Secar 71 and 10 g of PVA
inorganic bond whose function can be substituted by the GH-17s were weighted, and subsequently the mixture was
ceramic bond during the actuation of high temperature when mixed by the conventional planetary mixer for 5 min. Mean-
working. while, the solution was prepared from exact volume of distilled
A typical example of unshaped refractory materials with water and glycerol as a plasticizer (Table 3). The solution was
inorganic bond is calcium aluminate cements and refrac- added to the mixture of PVA and cement. Finally, the sample
tory concretes made of them. During the setting and was mixed again thoroughly and transferred to high-shear mixer.
hardening clinker minerals of calcium aluminate cement,
mainly CaOAl2O3 and CaO2Al2O3, gradually dissolve High-shear mixing
and new crystalline calcium aluminate hydrates of hexag-
onal (e.g., 2CaOAl2O38H2O, CaOAl2O310H2O, Twin-roll mixer (see Figs. 1, 2) was used for a more thor-
4CaOAl2O313–19H2O) or cubic (3CaOAl2O36H2O) ough homogenization and high-shear processing of the
structure and colloidal gibbsite (Al(OH)3) precipitate from
the solution [1]. When refractory material is working, all of
the hydrates loose its crystalline water in temperature range Table 1 Properties of calcium aluminate cement Secar 71
from 100 up to 350 C which is joined with a significant Common range/ Specific limit/
volume decrease leading to local stresses in the material mass% mass%
structure released by formation and growth of cracks.
Chemical composition
Compared to the calcium aluminate cement concrete, the
Al2O3 68.7–70.5 [68.5
MDF composite should not exhibit so high shrinkage
CaO 28.5–30.5 \31.0
because the hydration degree of cement in hardened MDF
SiO2 0.2–0.6 \0.8
composite is very low.
Fe2O3 0.1–0.3 \0.4
The MDF composites cannot be used as the unshaped
TiO2 \0.4 –
refractory material, because it has to be well high-shear
processed and then formed into the required shape. The MgO \0.5 –
excellent shaping properties of MDF composites in the Na2O ? K2O \0.5 –
fresh state enable to make uncommon products of unusual SO3 \0.3 –
shapes and properties for refractory industry. Mineralogical composition
Main phase CA, CA2
Secondary phases C12A7, a-A
Experimental Fineness
Specific surface/cm2 g-1 3,800–4,400 [3,500
Materials Over 90 lm/% \5
Setting time
MDF composite samples were fabricated using the process Setting beginning/min 190–240 [165
developed by Birchall et al. [18] and optimized by Russell Setting end/min 200–260 \300
[19]. The components ratio was optimized for the used type Compressive strength/MPa
calcium aluminate cement Secar 71 (Lafarge Aluminates) After 6 h 15–30 [10
(Table 1), polyvinyl alcohol Gohsenol GH-17s (Nippon After 24 h 40–55 [30
Chemicals) (Table 2) and glycerol.

MDF composites preparation

Table 2 Properties of polyvinyl alcohol Gohsenol GH-17s

The composition and the volume of the particular compo- Material properties Value
nents for the new MDF composite have been considered as
Hydrolysis degree/mol% 87.6
the main factors affecting the properties of materials. The
Viscosity (4 % water solution)/mPas 29.1
basic assumption was proposed by literature [19] and
Volatiles/mass% 3.7
experimented consequently. The basic premise was the
pH (4 % water solution) 5.7
good workability and the suitable mixture amount during
Melting point/C 150–230
the preparation. The procedure of MDF composite con-
Density (20 C)/g cm-3 1.19–1.31
sisted of the following steps:

123
High temperature properties of MDF composite 1247

Table 3 Composition of MDF composite

Component Composition
/g /mass%

Calcium aluminate cement Secar 71 200 80.5

PVA Gohsenol GH-17s 10 4.0
Glycerol 2.5 1.0
Deionized water 36 14.5

mixture as well as the preparation of specimens. The mixing Fig. 1 Twin-roll mixer processing the MDF composite paste (left)
is important to achieve intimate contact between the poly- and scheme of mass movement between the rolls during the high-
mer, water, and cement. The twin roll mixer consists of two shear stress
movable rolls with a gap of 3 mm, approximately. Another
part of the two copper spatulas prevents the material reach
edges of rollers. Further, it maintains a small excess of
material in the working space, which supports ‘‘high-shear’’
effect. High-shear mixing took place 10 min.

Flexural strength measurement

A flexural strength and modulus of the heated MDF com-
posite specimens was tested on apparatus ZWICK ROELL
010. Three-point bending test was used to determine the
flexural strength of formed materials. With regard to the
used twin-roll mixer and the limited 3-mm thick paste plate
removed from the bigger cylinder of the mixer. The paste
plate was pressed under 10 MPa for 1 min to smooth the
plate surface at the earliest. Afterwards, specimens of
20 9 50 mm were cut from the plate (Fig. 1). The prepared
specimens were further heated in the muffle furnace up to
240, 300, 600, 1,000, and finally 1,500 C with heating rate
5 C min-1 and 1 h isotherm at the temperature followed by
a spontaneous cooling. The mentioned temperatures were
chosen after previous experiments and they stand for the
distinctive stages between the processes that take place
during the thermal treatment of MDF composite as it will be
seen in ‘‘Results and discussion’’ section.
This thin-wall testing samples are not certified so the
setup of testing machine ZWICK ROELL 010 was adjusted
to these untypical samples: 5 mm radius of loading and
supporting blades, test speed 1 mm min-1, pre-load 5 N
and supports spacing 40 mm. To get statistically well-
supported data samples were measured five times at least
and its arithmetical average and standard deviation were
calculated.
TG–DTA–EGA
Combined thermal analysis technique–differential thermal
analysis (DTA), thermogravimetry (TG) (TA Instruments
Q600) and effluent gas analysis (EGA) (FT-IR Thermo
Nicolet iS10) was utilized for better understanding of the
Fig. 2 Samples for three-point bending test
structure of prepared modified MDF composites before and
after thermal treatment. The experiments were carried out
from 30 to 1,000 C using 10 C min-1 temperature ramp
under dried air atmosphere. The gas chamber and the
transfer capillary was heated to 200 C and FT-IR spectra
of evolved gasses were collected with following setup:
spectral range 600–4,000 cm-1, spectral resolution
8 cm-1, spectra measurement interval 19 s.
Thermomechanical analysis
Thermomechanical analysis was carried out in the three-
point bending experimental setup using instrument Setaram
Setsys EVO 2400. The samples of dimensions approx.
3 9 3 9 14 mm (height 9 width 9 length) (the exact
dimensions were measured and used in calculations) was
adjusted on the corundum supports of 12 mm spacing, and
the corundum rod was placed in its center with 5 g (0.05 N)
pre-load. The sample was heated up to 1,500 C with
5 C min-1 heating rate under inert argon atmosphere of
30 mL min-1 flow rate and under constant bending force of
1.00 N. The acquired data was plotted as the influence of
temperature on bend of the specimen, and it was also used
for calculation of flexural modulus using Eq. 1:
l3  F
E¼ ; ð1Þ
4  w  h3  d
where E is flexural modulus, l is supports spacing, F the
applied force, w the specimen width, h the specimen height,
and d is the specimen bend. Afterwards, the calculated elastic
modulus was plotted as a function of temperature.

123
1248 F. Šoukal et al.

Heating microscopy 0.6 105

Deriv. mass/mass% °C–1

0.4 0.06
The beginning of sintering during the firing of MDF com- 100

posite was determined using heating microscope Hesse

Heat flow/W g–1

Mass/mass%
0.2 0.04
Instruments EM-201. Sample of a cubic piece of non-grinded 95
MDF composite of 3 9 3 9 3 mm was used for the mea- 0.0 0.02

surement up to 1,550 C with heating rate 5 C min-1, and

90
the sample data was collected for each 10 s. The measure- –0.2 0.00

ment was repeated three times, and the data were averaged.
–0.4 85
0 200 400 600 800 1000 1200 1400 1600

Scanning electron microscopy Exo up

Temperature/°C

Fig. 4 TG, DTG, and DTA curves of MDF composite

The observation of fracture surfaces and cross-sections of
hardened and also fired samples of MDF composite was
carried out at scanning electron microscope JEOL JSM 0.04
H2O
0.07

7600-F in backscattered observation mode. The cross-sec- 0.03 0.15 CO2

H2O 0.06

tion was prepared by mechanical polishing and all samples 0.03

0.10
CO2
0.05
were coated with thin layer of gold. 0.05

Relative intensity

DTG/mass% K–1
0.02 0.00 0.04
1000
3500
3000
Results and discussion 0.02 2500
2000 500
0.03

Wavelength/cm–1 1500 Temperature/°C

1000
0.01 0.02

Mechanical properties 0.01

0.01

0.00 0.00
The results of measurement of flexural strength and modulus 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500

in three-point bending are reported in Fig. 3. The flexural –0.01 Temperature/°C –0.01

H2O CO2 DTG

strength and modulus dependence versus temperature of fur-
nace are plotted. The decrease of flexural strength with tem-
perature is evidenced. The most noticeable strength drop takes
place between the laboratory temperature and 240 C from
79.2 to 25.4 MPa followed by further decrease at 300 C to
12.7 MPa. The strength after heating at 600 and 1,000 C
decreases yet only little to 10.1 and 9.2 MPa, respectively,
whereas the firing at temperature 1,500 C leads to an increase
of flexural strength up to 54.6 MPa. The flexural modulus
dependence shows the same trend as the strength, but the
initial decrease at 240 C is not so significant.
90
Fig. 5 EGA results of MDF composite
Thermal analysis
The obtained thermogravimetric, derivative thermogravi-
metric, and heat flow curves are plotted in Fig. 4. Release
of water vapor and carbon dioxide during the thermal
analysis (relative spectral intensities at wavelength
1,507 cm-1, resp. 2,359 cm-1) is plotted together with
DTG curve against the temperature in Fig. 5. The first
endothermic effect with mass loss rate maximum at 145 C
is connected with evaporation of unbounded capillary and
gel water within the polymer–inorganic gel matrix. This

80 79.2
water evaporation is followed by the next one with a
70
maximal rate at 205 C caused by dehydroxylation of
60
polyvinyl alcohol. Afterwards, these water evolving pro-
54.6
50
cesses gradually decrease up to 580 C with one small rate
40
40.3 increase at 282 C [20] . The DTG maximum at 282 C
30 25.4
connected with small endotherm at 289 C, and it is caused
21.9
20
19 by dehydration of calcium aluminate hydrates [1]. The
12.7 13.2
10
10.110.5 9.2 8.8 oxidation of polyvinyl alcohol starts at 190 C and it has
0
20 240 300 600 1000 1500
the maximal rate at 347 C. The oxidation produces carbon
Temperature/°C dioxide and water vapor and it runs in two partially over-
Flexural strength/MPa Flexural modulus/GPa
lapping steps up to 580 C characterized with strong exo-
Fig. 3 Dependence of flexural strength and modulus of MDF thermic effect with maximum at 339 C. Between 580 and
composite on temperature 700 C only the carbon dioxide evolution is running out

123
High temperature properties of MDF composite 1249

due to the oxidation of pyrolysis carbon perhaps. Further softens with increasing temperature [21]. In the tempera-
carbon dioxide evolution is caused by decomposition of ture range 100–245 C, even significant loss of modulus
carbonates with maximal rate at 859 C. No more gases continues within two steps of maximal rates at 156 and
evolution connected with decomposition processes is 215 C, respectively. These temperatures are in a good
observed up to 1,500 C. agreement with temperatures of maximal rates of evapo-
ration of free capillary and gel water (143 C) and poly-
Thermomechanical analysis vinyl alcohol dehydroxylation (203 C), respectively. The
rapid modulus decrease ends at 245 C (Fig. 6) when the
The calculated flexural modulus from bending TMA oxidation of polyvinyl alcohol begins. The loss progresses
measurement was plotted as a function of temperature in only slowly up to the temperature 369 C which corre-
Fig. 6 supplemented with the first derivation of this curve sponds to the maximum of polymer oxidation rate
that better highlights the particular steps of the flexural (347 C). Between 369 and 823 C, the flexural modulus
modulus decrease. It is obvious that the strongest decrease remains constant because the polymer in matrix is just
of flexural modulus takes place at low temperatures below degraded, and the pyrolysis products cannot play a struc-
100 C. This drop of modulus cannot be associated with tural role any more. Only the oxidation of pyrolysis pro-
the drying of the composite matrix gel because it should ducts continues up to 700 C (Fig. 5). The temperature
increase the modulus. But the MDF composite exhibits 823 C was evaluated as the beginning of the next drop of
strong dependence of flexural modulus on temperature in flexural modulus ending at 939 C caused by decomposi-
the temperature range because the composite matrix is tion of carbonates. Further loss of flexural modulus starts at
composed mainly of polymer–polyvinyl alcohol that has 1,131 C and proceeds with the slope 0.11 MPa K-1 up to
glass transition temperature about 40 C and gradually 1,351 C and then the slope decreases to 0.06 MPa K-1 in

Fig. 6 Dependence of flexural 2000

modulus on temperature 0
1750
calculated from TMA 550 0

measurement 1500
500 –1

dFlexural modulus/MPa s–1

450

dFlexural modulus/MPa s–1

400 –0.5
–2
Flexural modulus/MPa

1250
Flexural modulus/MPa

350

300
1000 –1 –3
250

200
750 –4
150 245.2 (°C)
823.5 (°C)
1130.9 (°C) –1.5
100 369.1 (°C)
500 939.0 (°C)
50 –5
1350.9 (°C)
0
250 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Furnace temperature/°C –6

0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500
Furnace temperature/°C

Fig. 7 Percentage change of 100

specimen profile area
98

96
Specimen area/%

94

92

90

88

86

84
0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600
Temperature/°C

123
1250
Fig. 8 SEM images of fracture
surfaces and cross-sections (in
corners) of MDF composite at
20 C (a) and heated at 240 C
(b), 300 C (c), 600 C (d),
1,000 C (e), 1,500 C (f)
the presence of melt and continues up to 1,500 C the final
temperature of measurement.
Heating microscopy
The Fig. 7 shows the specimen profile area measured using
heating microscope as a function of temperature. The
results show initial shrinkage of 2 % caused by drying of
the composite matrix up to 250 C approximately. The
further small area increase is caused by the recrystallization
process of CA from the amorphous product of the foregone
dehydration of calcium aluminate hydrates. The tempera-
ture of beginning of sintering has been determined from the
graph at 1,450 C that is about 5 % of the specimen area
decrease. This finding is in correlation with the flexural
strength increase after firing the MDF composite at
1,500 C (see Fig. 3) which the new ceramic bond must be
responsible for. Finally, the specimen area decreased to
87 % at 1,565 C that indicates slowly continuing sintering
of the material below the temperature.
123
F. Šoukal et al.
Scanning electron microscopy
Figure 8 shows the evolution of microstructure of MDF
composites thermally treated at different temperatures. The
particular SEM images in Fig. 8 represents the microstructure
at the distinctive temperatures 20, 240, 300, 600, 1,000, and
1,500 C seen in the fracture surfaces and the cross-sections (in
the corners). The structure of non-heated MDF composite is
the typical one—unhydrated cement grains (the brighter ones
are CA and the darker ones are CA2 in the backscatter imaging
mode) surrounded with the cross-linked polymer matrix con-
taining cement hydration products [9]. The matrix is very
dense and compact and well bounded to the cement grains.
While the microstructure of MDF composite heated at 240 C
is apparently porous and tends to be uncompact. At this stage,
the free water from the matrix is gone out and the dehydr-
oxylation of polymer is achieved and the cross-linking bonds
deterioration begins [10, 12, 13]. Such a difference of the
microstructure compared to the initial state clarifies the rapid
flexural strength decrease at this temperature (see Fig. 3). The
High temperature properties of MDF composite
polymer matrix does not function as the strength and ductile
material that dissipates the local stresses under the load and
eliminates the crack formation and propagation any more. The
structure at 300 C is very similar to the previous one. The
dehydration of cement hydrates occurred at this temperature as
mentioned above. Because the calcium aluminate hydrates are
dispersed within the matrix in form of nanoparticles [9], the
microstructure of the matrix observed by SEM is not visibly
affected by this process. The cross-linking of matrix is dam-
aged at this temperature [10, 12, 13] that further deteriorates
the mechanical properties. The next important state of material
transformation during the thermal treatment is after the com-
plete polymer pyrolysis and oxidation at 600 C. The micro-
structure of matrix is even more porous and uncompact, and
tends to split up into each other incoherent agglomerates. The
microstructure at 1,000 C after decomposition of calcium
carbonate has almost the same character as the previous one.
Only the small submicron particles remaining in matrix after
the polymer burnout look rounded. The last SEM image is
shows the microstructure of MDF composite after firing at
1,500 C. It is obvious that the sintering takes place at this
temperature creating a porous but very coherent structure. That
leads to the new increase of flexural strength to high values
after cooling down (see Fig. 3).
Conclusions
The material behavior and the processes taking place during
thermal treatment of MDF composite based on calcium
aluminate cement and polyvinyl alcohol has been examined.
The obtained results can be resumed in the following points:
• MDF composite loses the flexural strength and modulus
mainly after heating to 240 C. This is joined with the
desiccation of polymer matrix, dehydroxylation of
polyvinyl alcohol, and beginning decomposition of
cross-linking bridging bonds within the matrix. The
loss of modulus at temperatures below 100 C occurs
due to gradual softening of polymer after glass
transition temperature at about 40 C.
• Flexural modulus decreases only little at temperatures over
250 C. The particular flexural modulus drops are connected
with the matrix cross-links decomposition, the pyrolysis and
oxidation of polyvinyl alcohol, the decomposition of
calcium carbonate, and the beginning of sintering.
• The flexural strength after heating at 1,500 C returns
to high values near the initial state due to sintering and
formation of ceramic bond.
• The acquired results confirm the assumed application
potential of MDF composites based on aluminate
cement for special refractory applications where their
shaping possibilities will be valorized.
1251
Notation
The following silicate chemistry notation is used in this
article: C = CaO, A = Al2O3, H = H2O.
Acknowledgements This work has been supported by project of
Ministry of Education, Youth and Sports of the Czech Republic No.
CZ.1.05/2.1.00/01.0012 ‘‘Centre for Materials Research at FCH
BUT’’ supported by operational program Research and Development
for Innovations.
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