Materials Science Forum Submitted: 2015-12-08

ISSN: 1662-9752, Vol. 865, pp 95-106 Revised: 2016-03-07

doi:10.4028/www.scientific.net/MSF.865.95 Accepted: 2016-03-17
© 2016 Trans Tech Publications, Switzerland Online: 2016-08-11

Sulfate Resistance of Alkali Activated Cements

KRYVENKO Pavlo1, GUZII Sergii2, *, KOVALCHUK Olexandr3
and KYRYCHOK Volodymyr4
1-4
V.D. Glukhovskii Scientific Research Institute for Binders and Materials, Kyiv National University
of Construction and Architecture, Povitroflotskii prospect, 31, Kyiv 03037 Ukraine
* sguziy@ukr.net

Keywords: Aggressive Environment, Coating, Concrete, Fly Ash Alkali Activated Hybrid Alkaline
Cement, Geoсement, Hydration Products, Sulfate Resistance.

Abstract. One of the most important questions of concrete durability is increasing of corrosion
resistance of cement stone and materials on his basis. Perspective way of solving such problems is
using of alkali activated binders.
Two cement systems were investigated to obtain different materials for different application -
geocement system for repair materials and protective coatings and fly ash alkali activated hybrid
cement for corrosion resistant common cements and concretes.
It was studied sulfate resistance of fly ash alkali activated cements after 3 years of storing in
aggressive environments like 5 and 10 % solutions of sodium sulfate, 2 and 4 % solutions of
magnesium sulfate and sea salt solution. It was shown that fly ash containing cements are
characterized by high corrosion resistance (coefficient of corrosion resistance after 3 years of storing
in aggressive environment is in the ranges 0.8...1.0) comparing with clinker cements (0.45...0.88).
Shown, that high sulfate resistance of cements under study in time is caused by graduate structure
development and crystallization of new formations with compacting structure of material that effect
on service properties of materials.
High corrosion resistance of geocement compositions (coefficient of corrosion resistance 0.9-1.05) in
sulfate environment is possible because of formation of faujasite, chabasite, mordenite and nozean
phases in the structure of materials. Optimal composition of geocement compositions were developed
according mathematical planning of experiments and tested.

Introduction
At present time there are many materials are offer in the market. However, we still have problems
with durability of materials, especially in special exploitation conditions like aggressive environment
and so on. According to [1-3] about 20-25% of yearly cement production are using for repairing of
exist constructions and materials. Present material all have some disadvantages - some of them have
difficult technologies, some are very expensive and could not be used for common application, some
do not met requirement of resistance in different environment. Nowadays clear position is taken that
there are no universal material for any application in aggressive environments. So, industry needs to
have a new effective materials to be used as corrosion resistant materials as in common constructions,
so as in repair mixes and protective coatings.
Fundamental studies of SRIBM researchers in the field of direct structure formation and properties
of alkali activated cements and concretes on their basis make it possible to widely expend possible
area of application of such materials in different branches of construction and industry [4-12].
Possibility to achieve corrosion resistant alkali activated cements was proved for a several times.
Increased resistance in aggressive environments of alkali activated cements (AAC) based on fly ashes
and slags is provided by synthesis in microstructure of artificial stone low basic hydro silicate and
alkaline aluminasilicate fazes like nosean (Na8Al6Si6O24(SO4)), which are able to fill pores of cement
stone prevent growth of sulfate aggression, that was shown in different studies [13-16].
Following studies in this direct shows that introduction of metakaolin and fly ash to the alkali
activated cement compositions led to obtain concretes with more dense structure and higher acid

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96 Binders, Materials and Technologies in Modern Construction II

resistance in the ranges of pH value from 1 to 3 [4-8]. Concretes on their basis are effective for
industrial and agricultural applications, but not common as repair compositions.
Studies [9-12] suggested showing that for repair activities the most common is using of geocement
compositions. It is possible to make synthesis of high silica phases (SiO2/Al2O3>5), able to be
resistant in aggressive environments (Table 1).

Table 1. Stability of synthetic zeolites in acids

Zeolite type SiO2/Al2O3 Resistance to acids
Na-A 2.0 Soluble at pH<5
Na-X 2.4-2.7 Soluble at pH<5
Na-Y Below3.5 Deteriorates in 3N-acetic acid
Na-Y 4.0-5.9 Slightly deteriorates in 3N-acetic acid
Na-E 6.0 Slightly deteriorates in 3N-acetic acid
Na-M 10.0 Not deteriorates in 3N-acetic acid

However, geocement compositions cannot be use for common cements and concretes on their
basis. That is why a huge interest now it is paying for fly ash alkali activated cements. Many studies
show high corrosion resistance of such materials.
However, despite the positive results of fly ash AAC corrosion resistance, one of the breaking
factors of wide application of such materials is that were no studies of long-term storing in aggressive
environment, so there is no possibility to predict stability of fly ash AAC based concretes properties
on later stages of hardening.
Purpose of study is investigation of genesis of structure and sulfate resistance of alkali activated
cements for different application areas ─ geocement compositions [17-23] and fly ash based hybrid
alkali activated cements [24-26].

Raw materials and methods of tests

For obtaining of geocements with structural formula Na2O·Al2O3·(6-8)SiO2·(20-30)H2O were used
soluble glass, metakaolin and microsilica. Calculated ratio of main oxide was SiO2/Al2O3=6...8 and
H2O/Al2O3=20...30.
Optimization of geocement composition and protective coatings was done by 2-factors 3-levels
method of experiment. As a main functions were taken corrosion resistance and speed of corrosion.
As a main component of fly ash AAC cements was taken low basic fly ash class F (according to
ASTM C 618), grinded to the surface 800 m2/kg, as alkaline component - sodium carbonate (technical
grade). For activation of the systems were used OPC Grade 52.5 with specific surface 380 m2/kg and
grinded blast furnace slag with specific surface 450 m2/kg. A surfactant with plasticizing effect was
use as modifying admixture. As composition to compare was taken slag OPC Grade 42.5. Chemical
composition of raw components is given in Table 2.

Table 2. Chemical composition of raw materials

SiO2 A12O3 Fe2O3 CaO MgO SO3 Na2O K2O Mass loses
Material
% % % % % % % % %
Fly ash 51.08 24.8 13.67 3.12 1.83 0.08 0.60 1.90 1.50
OPC 23.4 5.17 4.12 64.13 0.88 0.55 0.41 0.33 0.20
Slag 40.0 5.91 0.32 46.98 5.87 1.62 - - -
At present study were consider concretes based on fly ash AAC, classified according to [27]. As
alkali activated pozzolanic cement AAC III-3and alkali activated composite cement AAC V. AAC
were prepare by separate grinding of fly ash and slag and subsequent mixing of all the components
together with alkaline component and plasticizer during 3 min in the mixer for dry mixes preparation.
As a cement to compare was, take slag OPC. Compositions of cements are given in Table 3.
 Materials Science Forum Vol. 865 97

Table 3. Composition of fly ash alkali activated cements

Cement type Composition, % by mass
Fly ash OPC 52.5 Slag Alkaline Plasticizer CaSO42H2O
component
AAC III-3 66.2 28.4 - Na2CO3-4.7 0.7 -
AAC V 56.7 9.5 28.4 Na2CO3-4.7 0.7 -
PSC III/А - 64 36 - - 5

Studies of peculiarities of structure formation processes of the cement were done using complex of
physical-chemical (X-ray and SEM) and physical-mechanical methods of investigations on the
specimens of artificial stone.
For providing tests were prepared beams 10x10x70 mm from mortar with “cement: sand” ratio =
1:3 (water/cement ratio is taking according to paste of normal consistency). According to
recommendations [28] specimens were storied during 24 hrs in normal conditions and then after
remolding removed to the water. After 14 days of storing in water, specimens were put to the salt
solutions.

Corrosion resistance of concretes was determine according to the standard [29, 30] by calculation
changes of flexural strength in aggressive environment. Tests were don after 30, 60, 90, 180 days and
3.5 years storing in aggressive environment.
Coefficient of corrosion resistance was determined as a ratio between flexural strength of the
specimens storied for 12 months in aggressive environment to flexural strength of the specimens
storied for 12 months in water. According to the given method, specimens are corrosion resistant if
after storing in aggressive environment coefficient of corrosion resistance Kc > 0.8.
Average speed of corrosion, g/m2-hour, (corrosive losses of protective surface per time unit) was
calculate by formula:

, -- (1)
where: m0, m1, - mass of the specimen before and after tests on corrosion resistance
correspondently, g; So - surface of the specimen, m2; τ - duration of tests, hour.

Results and discussion

Geocement system
Optimization of geocement composition and protective coatings was done by 2-factors 3-levels
method of experiment. As main functions were, take corrosion resistance and speed of corrosion.
Matrix of experimental plan and test results are given in Table 4.
In result of provided modeling it were obtained equalities of regression, which explained
mathematical models Y1...Y6 of influence of quantity ration of oxides SiO2/Al2O3 and H2O/Al2O3 on
stability of geocement to the influence of resistance 5% solutions of sulfates.
Analysis of models Z1-Z2 shows that corrosion resistance, speed of corrosion and deepness of
geocement corrosion in 5% solution of sodium nitrate is mostly influenced by common action of
factors X11, X22 and X1X2; models Z3-Z4 - mostly influenced by factor X2 (H2O/A12O3).
98 Binders, Materials and Technologies in Modern Construction II

Table 4. Matrix of experimental plan and results of tests in the system

Na2O·Al2O3·(6-8)SiO2· (20-30)H2O
Planning matrix Type of corrosive environment ─ 5% solution
SiO2/ H2O/ Na2SO4 MgSO4 (NH4)2SO4
Al2O3, Al2O3,
X1 X2
8 30 0.48 0.79 0.57 0.87 0.88 0.074
8 20 0.62 0.96 0.39 0.93 1.01 0.131
6 30 0.98 0.43 1.00 0.52 1.10 0.189
6 20 0.75 0.54 0,90 0.66 0.92 0.617
8 25 0.49 1.09 0.33 0.58 0.96 0.069
6 25 0.81 0.45 0.73 0.91 0.79 0.073
7 30 0.61 0.74 0.50 0.90 0.74 0.177
7 20 0.68 0.70 0.61 1.16 1.03 0.907
7 25 0.58 1.13 0.,44 1.36 0.73 0.102
Analysis of data from Table 4 and Fig. 1 shows that highest corrosion resistance in sodium sulfate
─ Kc=0.75-1.0 are characterized geocements with oxides ratio SiO2/Al2O3=6-6.5 and
H2O/Al2O3=20-30 (Fig. 1, a), and lowered speed ─ geocements with oxides ratio SiO2/Al2O3=7 and
H2O/Al2O3=20-30 (Fig. 1, b).
a) b)

Figure 1. Surfaces of changes of corrosion resistance coefficient Кс (a), and speed of corrosion Кb
(b) of geocements composition Na2O·Al2O3·(6-8)SiO2·(20- 30)H2O in 5% solution of Na2SO4
In environment of magnesium sulfate highest corrosion resistance ─ Kc=0.9 and 1.0 take place for
geocements with SiO2/Al2O3=6 and H2O/Al2O3=20 and 30 (Fig. 2, a), and lowered speed of corrosion
0.52 g/m2hour for geocement with SiO2/Al2O3=6 and H2O/Al2O3=30 (Fig. 2, b). The highest
corrosion resistance in ammonium sulfate ─ Kc=0.9-1.1 have geocements with oxides ratio
SiO2/Al2O3=6 and H2O/Al2O3=20 and 30 (Fig. 3, a), and lowered speed of corrosion 0.074 g/m2hour
- geocement with SiO2/Al2O3=8 and H2O/Al2O3=30 (Fig. 3, b).
As it seems from Fig. 4, curve 1 geocement hydration products with oxides ratio SiO2/Al2O3=6 are
represented by heulandite-faujasite phases with some parts of chabasite, mordenite and sodalite.
At X-ray data there are present peaks of heulandite (Ca, Na2){Al2Si6O6}·5H2O (d=0.85; 0.67;
0.52; 0.45; 0.395; 0.35; 0.31; 0.293; 0.252; 0.245; 0.212; 0.197; 0.177; 0.174; 0.166; 0.160; 0.156
nm), faujasite Na2Ca{Al4Si10O28}·20H2O (d=0.74; 0.55; 0.48; 0.44; 0.38; 0.35; 0.301; 0.2602; 0.237;
0.217; 0.205; 0.197; 0.190; 0.174; 0.157 nm) and nosean (Na8Al6Si6O24(SO4)) (d=0.371; 0.286;
0.228; 0.178 nm).
 Materials Science Forum Vol. 865 99

a) b)

Figure 2. Surfaces of changes of corrosion resistance coefficient Кс (a), and speed of corrosion Кb
(b) of geocements composition Na2O·Al2O3·(6-8)SiO2·(20-30)H2O in 5% solution of MgSO4

a) b)

Figure 3. Surfaces of changes of corrosion resistance coefficient Кс (a), and speed of corrosion Кb
(b) of geocements composition Na2O·Al2O3·(6-8)SiO2·(20-30)H2O in 5% solution of (NH4)2SO4.

In small quantities there are present crystalline phases of hydro sodalite Na6(AlO2)(SiO2)6·8H2O
(d=0.3661; 0.1906; 0.1599 nm), chabazite (Ca, Na2){Al2Si4O12}·6H2O (d=0.683; 0.4821; 0.1559 nm)
and mordenite Ca0.71 Na 0.46{Al2(Al0.52Si9.59)O24}14.01H2O (d=0.3833; 0.1871; 0.1812 nm).
Microstructure of artificial stone with oxides ratio SiO2/Al2O3=6 (Fig. 5) is dense, fine crystalline
with well-observed mordenite needles, chabazite rhombus, plate crystals of heulandite and long pillar
crystals of faujasite. In case of increasing of oxides ratio SiO2/Al2O3 from 6 to 7 geocement hydilation
products have heulandite-faujasite-mordenite composition with some quantities of analcime, hydro
sodalite and chabasite. at X-ray pattern (Fig. 4, curve 2) were observed diffraction rising of huelandite
peaks (Ca, Na2){Al2Si6O16}·5H2O (d=0.876; 0.274; 0.2486; 0.2274; 0.2085; 0.1666 nm), faujasite
Na2Ca{Al4Si10O28}·20H2O (d=0.5682; 0.3310; 0.3094; 0.2873; 0.2613; 0.236 nm), mordenite
Ca0.71 Na 0.46{Al2(Al0.52Si9.59)O24}·14.01H2O (d=0.3833; 0.1871; 0.1812 nm) and nosean
(Na8Al6Si6O24(SO4)) (d=0.371; 0.286; 0.228; 0.178 nm).
Diffraction peaks rising of hydro sodalite and chabasite are the same as higher underlined,
analcime it is fixed at d=0.1828 nm.
100 Binders, Materials and Technologies in Modern Construction II

Figure 4. X-ray patterns of geocement stone after hardening at 80°C during 24 hrs with oxide
corresponded: 1 ─ SiO2/Al2O3=6; 2 ─ SiO2/Al2O3=7; 3 ─ SiO2/Al2O3=8; H2O/Al2O3=30. Marking:
H - heulandite; F - faujasite; NaM - mordenite; Sh -chabazite; GSc - hydrosodalite; N - nosean

Microstructure of artificial stone with SiO2/Al2O3=7 (Fig. 5) is dense, fine crystalline with
well-observed presents mordenite needles, plate crystals of heulandite and long pillar crystals of
faujasite.

SiO2/Al2O3=6; H2O/Al2O3=30

SiO2/Al2O3=7; H2O/Al2O3=30

SiO2/Al2O3=8; H2O/Al2O3=30

Figure 5. SEM photos of crack surface of geocement after hardening at 60°C during 24hrs
 Materials Science Forum Vol. 865 101

In case of increasing of oxides ratio SiO2/Al2O3 from 7 to 8 hydration products of geocement have
mordenite-chabisite-fuajasite composition with some quantities of heulandite, hydro sodalite and
analcime (Fig. 5). At X-ray pattern (Fig. 4, curve 3) it were observed peaks of high-silica mordenite
Na8{Al8Si40O96}24H2O (d=0.5743; 0.3198; 0.2889; 0.2706; 0.1809 nm), chabasite (Ca,
Na2){Al2Si4Oi2}·6H2O (d=0.683; 0.4821; 0.2889; 0.2613-0.2406; 0.1559 nm), faujasite
Na2Ca{Al4Si10O28}·20H2O (d=0.301; 0.237; 0.2158; 0.1903; 0.174; 0.1573 nm). Peaks of heulandite
and hydro sodalite are the same as underlined higher analcime Na{AlSi2O6}·H2O it is fixed at
d=0.4869; 0.3459; 0.1828 nm. Also it was mentioned reducing of nosean phase quantity
(Na8Al6Si6O24(SO4)) (d=0.371; 0.286; 0.288; 0.178 nm).
Microstructure of artificial stone with SiO2/Al2O3=6 (Fig. 5) is dense, fine crystalline with
well-observed mordenite needles, plate crystals of heulandite and lond pillar crystals of faujasite.
Taken results lay as a basis for obtaining protective coatings on geocement. Taking into account
that geocement with oxide ratio SiO2/Al2O3=6 is a most stabile to sulfate ions influence, for the next
activities and application it was chosen composition Na2O·Al2O3·6SiO2·30H2O.
However, geocement systems are very expensive and characterized by difficult technology of
preparation, so they can’t be used as common cements. They are able to be used for special kind of
application with high demands for service properties. For common application it is better to use fly
ash based alkali activated cements (hybrid cements).
References are cited in the text just by square brackets [1]. (If square brackets are not available,
slashes may be used instead, e.g. /2/.) Two or more references at a time may be put in one set of
brackets [3, 4]. The references are to be numbered in the order in which they are cited in the text and
are to be listed at the end of the contribution under a heading References, see our example below.

Fly ash based alkali activated hybrid cement system

Studies on corrosion resistance of alkali activated pozzolanic and composite cements were done in
the next aggressive environments:
- sea salt solution (salt concentration 1.8 % by mass);
- sodium sulfate solution (concentration 5 and 10 % by mass);
- magnesium sulfate solution (concentration 2 and 4 % by mass).
Results of physical-mechanical studies are shown on Fig. 6, where could be admitted that all
compositions after storing for 30 days in aggressive environments increase strength properties
comparing to analogues in water, that could be explained by deeper hydration level. But at the age of
2-3 months for most systems starts decreasing of strength, and at the age of 6 months compositions
based on slag OPC had their coefficient of corrosion resistance below 0.8 and failed tests.
At the age of 3.5 years (42 months) of storing in aggressive environment strength of fly ash based
AAC is still rising. Highest strength properties for the cement AAC III-3 were observed in 5% sodium
sulfate solution (12.2 MPa) and for the cement AAC V - in 2% MgS04 solution (14.8 MPa). Reducing
of strength for all fly ash based AAC obtained in 4% MgSO4 solution, (8.3 MPa). Artificial stone of
slag OPC was characterized by rising of strength in water, but in 10 % Na2SO4 solution and 4 %
MgSO4 solution its strength drops down to zero.
Obtained results of corrosion resistance coefficient (Table 1) let us admit that comparing to slag
OPC fly ash based AAC are good resistant. At the age of 9 months coefficient of corrosion resistance
of AAC do not fall lower then 1, at the age of 12 months composite cement in any case saves satisfied
strength (corrosion resistance coefficient in about 1.0 or higher), and the same coefficient of
pozzolanic cement decreases lower than critical level (0.8) only in 4% of magnesium sulfate
environment. Such result could be explained by constructive nature of alkaline activation of fly ashes
and formation of corrosion resistant new formations with mixed Ca/Na hydrosilicates nature (hybrid
cements).
Analyzing taken results of corrosion resistance after storing in aggressive environment for 42
months (Table 5) it could be mentioned that in comparison to slag OPC fly ash based AAC are
characterized by high corrosion resistance coefficient - 1.20.
102 Binders, Materials and Technologies in Modern Construction II

Table 5. Coefficient of corrosion resistance of concretes

Coefficient of corrosion resistance Kc after storing for
12/42 months in solutions
Cement type
10 % -
Sea salt 1 . 8 % 5 % -Na2SO4 2 % - MgSO4 4 % - MgSO4
Na2SO4
AAC III-3 0.95/0.80 1.00/1.20 1.45/1.14 0.90/1.04 0.74/0.43

AAC V 1.39/1.11 1.15/1.22 1.40/1.10 1,18/1.38 1.06/0.79

PSC III/A-400 1.05/0.86 0.88/0.20 0.80/0.00 0.77/0.78 0.71/0.00

а) water b) sea salt solution

c) Na2SO4 solution - 5 % d) Na2SO4 solution - 10 %

e) MgSO4 solution - 2 % f) MgSO4 solution - 4 %

Figure 6. Diagrams of flexural strength changes of concretes under influence of aggressive

environment: 1 ─ AAC III-3-400; 2 ─ AAC V-400; 3 ─ PSC III/A-400
Thus, for pozzolanic cement (system “fly ash - OPC - alkaline component”) corrosion resistant
coefficient is within the ranges 0.8... 1.20, and for composite cement (system “fly ash - grinded blast
furnace slag - OPC - alkaline component”) ─ Kc = 0.79... 1.38. Reducing of AAC is observed only in
4% MgSO4 solution, so in this environment cements under study are not corrosion resistant.
 Materials Science Forum Vol. 865 103

According to XRD analysis results phase composition of AAC new formations at the age of 28
days are represented mainly by low crystallized low basic calcium hydro silicates CSH (B) ( d = 0.304;
0.2764; 0.210; 0.184; 0.181; 0.168 nm), also could be fixed zeolite-like new formations like
gismondine with low intensity ( d = 0.188; 0.273; 0.274; 0.418; 0.191 nm) ads some rests of quartz
( d = 0.424; 0.335; 0.252; 0.245; 0.247, 0.212 nm) from fly ash composition. Results of XRD analysis
confirmed by results of thermal analysis ─ on the DTA curve was fixed double reflex at
135°C...210°C, that could victim about presence of low basic hydro silicates and gismondine.

a) b)
DTG
1
2
3
4

5
6

360 DTA

910 1
445 940
365
790 900
2
370
420
180 770

148

390 940
770 3
795
135
900
750 4
450
360 900
5
210 360 443
800
410
165 965
750
6
780

160
0 TG

10

1
15 4
36
% 25

Figure 7. X-ray (a) and thermal (b) analysis results of artificial stone of fly ash alkali activated
cements: 1, 2, 3 ─ AAC III-3; 4, 5,6 ─ AAC V, after 28 days of hardening (1,4), 90 days (2, 5) and
3.5 years of hardening (3, 6)

At the age of 90 days phase composition of new formations of fly ash AAC significantly not
changes. Crystallization level of new formations represented by hydro silicates and gismondine grows
up a little, but even at this age there are forming carbonate compositions (calcite). Such results of
phase structure are matching results of other scientists work [11-14], where were shown that results of
hydration in such systems could be represented by C-S-H, N-A-S-H and (N,C)-A-S-H gels with the
following crystallization from them low basic calcium hydrosilicates and zeolite-like phases. Typical
hydration and re-crystallization product is calcite, appearance of which is a constructive process,
which is promoting structure compacting and increasing of service properties of material.
At the age of 3.5 years it is present partial re-crystallization of new formations - on XRD patterns 2
and 4 aside from calcium hydro silicates CSH (B) and gismondine Ca2Al2Si2O8·4H2O it is found
intensification of carbonate-type formations ( d =0.382; 0.304; 0.228; 0.209; 0.187 nm). Results of
XRD analysis are confirmed by thermal analysis results -thermal effects at 780°C...860°C and 975°C.
About recrystallization processes of gel and crystalline CSH phases in hydrated system and changes in
morphology of structure forming compounds with hydrosilicate composition, connected with
increasing Ca/Si ratio, victims shift to the lowered temperatures of effects from 201C ...180°C for
the systems at the age of 28 and 90 days to 160...120°C for the systems at 3.5 years of hardening.
104 Binders, Materials and Technologies in Modern Construction II

Reducing of cements mass loses after 42 months of hardening comparing to 28 days victims about
increasing of new formations crystallization level.
On micro photos (Fig. 8) it is observed fine dispersive structure of artificial stone, at 28 days there
are present not-hydrated rests of fly ash, in intergranular space are present needle like crystals,
accreted together, that victims about formation of low basic calcium hydro silicates. At the age of
3.5 years oh hardening artificial stone represents conglomerate, consisting from different parts of
microstructure without visible borders between granules of raw fly ash and parts with calcium
hydrosilicate.

a) b)

c) d)

Figure 8. SEM photos of fly ash alkali activated cements artificial stone: a, c ─ AAC III-3 and b, d
─ AAC V at the age of a, b ─ 28 days; c, d ─ 42 months of hardening

Conclusion
The main conclusion could be done that alkali activated cements in general are corrosion resistant
and have higher service properties in aggressive environments comparing with traditional analogues.
Corrosion processes, changes in microstructure and properties of alkali-activated cements were
investigated. The most interesting types of alkali-activated cement for creation of corrosive resistant
materials are fly ash AAC and geocements.
It was studied genesis of structure development of fly ash AAC and shown that together with low
basic calcium hydro silicates are forming zeolite-like hydro aluminasilicates and calcite, which are
providing higher crystallization range at the latest stages of hardening. This promotes formation of
artificial stone with uniformly shared crystalline structure that provide high density, strength and, as a
result, higher sulfate resistance.
It was shown that fly ash AAC after storing for 3.5 years in aggressive sulfate environments is
characterized by high corrosion resistance coefficient: for AAC III-3-400 ─ Kc = 0.8... 1.20, for AAC
V-400 ─ Kc = 0.79...1.22, significantly overreaching properties of slag OPC.
Influence of 5% solutions of sodium and magnesium nitrates on corrosion resistance of
geocements was studied. Materials on their basis could be used for repairing and ptotection of
concrete constructions. It was investigated, that the most stabile phases in sulfate environment are
faujasite, chabasite, mordenite and nozean, less stabile - heulandite and hydro sodalite. Speed of
corrosion of geocement in different sulfate environments was tested. In addition, it was shown that
chosen geocement composition Na2O·Al2O3·6SiO2·30H2O is corrosion resistant and characterized by
 Materials Science Forum Vol. 865 105

coefficient of corrosion resistance 0.9-1.05. Sulfate environments could be classified by aggressive

influence as a line: (NH4)2SO4>Na2SO4>MgSO4.
Geocement systems could be recommended for manufacture materials with specific properties (for
example, for creating coatings of high-temperature equipment. Hybrid fly ash based AAC are
recommended for civil engineering and materials with specific application both.

References
[1] Krivenko, P.V.: Alkaline Cements: Terminology, Classification, Aspects of Durability Proc.
10th ICCC Goteborg 1997, p. 4iv046-4iv050.
[2] P.V. Krivenko, A. Fernandez-Jimenez, A. Palomo: Classification and characteristics of alkali
activated cements J. Ceramic Society 40 (1) (2012), pp. 69-75.
[3] A. Palomo, P. Krivenko, I. Garcia-Lodeiro, E. Kavalerova, O. Maltseva, A.
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[8] Krivenko P.V. Ryabova A.G.: Ash alkaline binders Cements No11 (1990), pp. 14-16.
[9] Krivenko P.V.: Fly ash - alkali cements and concretes Proc. Fourth CANMET-ACI Intern.
Conf. on Fly Ash, Silica Fume, Slag and Natural Pozzolans in Concrete Istanbul (Turkey) 1992, pp.
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[10] Krivenko P.V., Skurchinskaya J.V.: Fly ash containing geocements Proc. Intern. Conf. On the
Utilization of Fly ash and other Coal Combustion By-Products Shanghai (China) 1991, pp. 64-1
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[11] O.S. Kavalerova, E.K. Pushkarova, V.I. Gots, G.Yu. Kovalchuk: Sustainable Development
through the Use of High-Volume Fly Ash Cements Proc. 16th Intern. Conf. “Ibausil”, Weimar
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[12] Krivenko P.V., Kovalchuk G.Yu.: Fly Ash Based Alkaline Cements Proc. Intern. Conf. Alkali
Activated Materials - Research, Production and Utilization, Praha (Czech Republic) 2007, pp.
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[13] Winnefeld F, Leemann A, Lucuk M, Svoboda P, Neuroth M.: Assessment of phase formation
in alkali activated low and high calcium fly ashes in building materials. Constr Build Mater 24(6):
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[14] Oh J.E., Moteiro P.J.M., Jun S.S., Choi S. and Clark S.M.: The evolution of strength
andcrystalline phases for alkali-activated ground blast furnace slag and fly ash-based geopolymers.
Cem Coner Res 40(2) 2010, pp. 189-196.
[15] Provis J.L, Lukey G.C., van Deventer J.S.J.: Do geopolymers actually contain nanocrystalline
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106 Binders, Materials and Technologies in Modern Construction II

[16] A. Palomo, A. Fernandez-Jimenez, L.M. Ordonez, M.C. Naranjo, G.Yu. Kovalchuk: OPC-Fly
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[18] P.V. Krivenko, S.G. Guzii, E.S. Kavalerova, V. Petranek. Repair and protection of concrete
surfaces using temperature and corrosion resistant coatings Sbornik prispevku XXII Mezinarodni
symposium “Sanace 2012” Brno 2012, pp. 201-206.
[19] Krivenko P.V., Guziy S.G., Kyrychok V.I.: Geocement-based Coatings for Repair and
Protection of Concrete Subjected to Exposure to Ammonium Sulfate Advanced Materials Research
Vol. 923 (2014), pp. 121-124.
[20] P. Krivenko, S. Guziy, V. Kyrychok, V. Petránek: Repair and protection of concrete
constructions of manure removal system anticorrosive coating on geoсement-based. Sbornik
prednasek “Sanace betonivyh konstrukci 2014” XXIV mezinarodni sympozium 22-23 kvetna Brno
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[21] Guzii S., Kryvenko P., Kyrychok V.: Technological features of the application of
geocement-based coatings for protection of concrete from exposure of ammonium salts Proc. 8th
Intern. Conf. Analytical Models and New Concepts in Concrete and Masonry Structures (AMCM
2014) June 16-18 Wroclaw, Poland 2014, pp. 550-559.
[22] P. Kryvenko, S. Guziy, V. Kyrychok: Geocement-based coatings for protection of concrete
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