15th International Congress on the Chemistry of Cement

Prague, Czech Republic, September 16–20, 2019

Hydraulic binder based on granulated blast-furnace slag and

silica fume

Lubomir Jezo1,a, Jozef Mikusinec 1,b, Martin Palou2,c

1Povazska cementaren a.s., Ladce, Slovakia

2Department of Materials and Rheology, Institute of Construction and Architecture, Slovak Academy of

Sciences, Bratislava, Slovakia

[email protected]
[email protected]
c [email protected]

ABSTRACT
In this study is presented new hydraulic binder, which could be evaluated from ecologic viewpoint as
“the greenest cement in world”. The patent was granted in Slovak Republic in 2015, number 288323,
named Hydraulic binder based on granulated blast-furnace slag and silica fume.
If this two basic cement components, which are both practically unreactive, are suitable activated by
cement clinker at the level of 0,5 - 1% , can form a standard solidifying and hardening binder, which is
comparable with cements class 32.5 N. Which mean the compressive strength after 28 days of
hardening was up to 40 MPa. This silica fume binder, named in Povazska cementaren a. s. Ladce as
Ladcement, have extremely high strength factor. This is calculated as strength ratio [MPa] of this
binder per unit amount of used clinker [%], which reflects the degree of usability of a clinker in the
binder related to achieved strength. The values achieved in PCLA were up to 40 MPa / 1% clinker.
 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

1. THEORETICAL PART

Conventional cement binders, whether they are hydraulic cements according to (STN EN 197 – Cement.
Part 1 2005) or masonry cements (STN EN 413-1. Masonry cement. Part 1, 2015) according to STN EN
413-1, are based on the presence of a certain sufficient amount of Portland clinker (more than 20 % by
mass) containing at least 2/3 of calcium silicates (C 3S – tricalcium silicate: 3CaO•SiO2, and dicalcium
silicate 2CaO•SiO2), which after mixing with water react exothermically to form solid hydrated products
responsible for the strength development, structure integrity and durability of concrete. Research in
Považská cementáreň a.s. Ladce, Slovakia (PCLA) has shown that a similar (comparable) solid
structure can be obtained without the presence of Portland clinker whose production is highly energy-
intensive supplemented by a high CO2 emission. To initiate setting and hardening processes, a very low
content of clinker of about 0.25 % to 2 % by mass or another activator from the basic components listed
in STN EN 197 – Cement. Part 1, 2005 at a level less than 3 – 5 % by mass is sufficient. The Industrial
Property Office of the Slovak Republic in Banská Bystrica granted a patent (Patent Nr. 288323 2015) to
PCLA for this in 2015.

The background of the hydraulic binder according to this invention consists in the fact that 60 to 95 %
of is composed of finely ground water-cooled granulated blast-furnace slag (hereinafter referred to as
BFS) according to the conditions stated in (STN EN 15167-1 2006) and 5 – 40 % are made up of silica
fume (microsilica – hereinafter referred to as SiF) produced according to (STN EN 13263-1 Silica fume
for concrete – Part 1 2006). A necessary condition for achieving high standard compressive strengths
(CS) and bending tensile strength (hereinafter BS) is a highly active BFS (STN EN 15167-1 2006),
classified in three steps of activity according to (Utility model – SK 7219 2015). These steps being
defined by the Ground BFS Activity Coefficient – GBFSAC, the so-called Ladce coefficient Lc and
reported in (Patent Nr. 288323 2045). Lc is defined as the product of the three relevant properties of
Ground BFS: specific surface (hereinafter referred to as SS) measured according to (STN EN 196-6
1992), the modulus of basicity (Mb), which is related to the proportion of the basic oxides and acidic
oxides in the BFS (Asim 1992), and its mineralogical composition – the modulus of glassiness (Mg),
which is the proportion of the glassy phase in the BFS (Bárta R 1961, Brandštetr, J 1984). The Lc is
obtained according to (1)

GBFSAC = Lc = SS x Mb x Mg (1)

and is described in more detail in connection with the development of the heat of hydration and Vicat
initial setting time described in (Ježo L 2014). However, this two-component mixture (BFS and SiF) sets
considerably longer than standard cements, even longer than the BFS itself. In order to accelerate the
setting, 0.25 to 4 % of cement clinker, or 0.5 to 5 % of a finely ground mixture of calcium sulphates, or
a mixture thereof, or a substance containing CaO, Ca(OH)2, or fly ash according to (EN 450-1) with a
content of 5 – 10 % is added. In this case, this is a system that does not need C 3S or C2S to develop
hydration reactions, but exothermic hydration reactions are achieved by appropriate mixing of a
sufficiently finely ground suitable BFS with a suitable chemical and mineralogical composition and
specific surface of at least 350 m 2 kg-1. The optimization of the mutual weight ratio of the two major
components has to be carried out as a function of the Ladce coefficient described above. According to
the above criteria (Utility model – SK 7219 2015, Ježo L 2014), the suitability of BFS in the above
mixtures can be divided into the following categories based on the heat flow of hydration during their
hydration with water (Ježo L, 2014):

 highly active – the max. hydration peak of the exothermic reaction is 1 to 3 days, the initial
setting time (IST) is less than 1000 min.;
 medium active – the max. hydration peak of the exothermic reaction is within 7 days, the
initial setting time (IST) is below 2000 min.;
 lowly active – the max. hydration peak of the exothermic reaction is more than 7 days, the
initial setting time (IST) is more than 2000 min.

The second basic component of this binder, the SiF, has been known for many decades as a basic
component of cement and concrete (STN EN 197 – Cement. Part 1 2005, STN EN 206-1 Concrete
2014). Its positive properties in cement and especially in concrete have been thoroughly summed up by
Aitcin (Aitcin 2005) and others (Bache 1984, ACI2342-96). SiF is generally less heterogeneous, but its
quality is influenced by the quality of fuel used in the production of ferro-silicon. The only manufacturer
in Slovakia is Slovenské ferozliatinárske závody in Istebné; all the SiF used in the series of more than
 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

100 experiments comes from this manufacturer. Several Slovak studies (Madej 1987, Slanička 1987,
Ježo 2008) deal with this SiF and its suitability for cement and concrete. This basic two-component
system generates sufficiently high compressive strength (CS) requested by standards according to (STN
EN 196-1 2006) after 28 days of curing, but especially after 180 and 365 days of hardening. In standard
(STN EN 196-3 2017), with CS requirements at lower levels of 12 to 20 MPa, but after 28, 180 and
365 days, the strengths are sufficiently high above 40 MPa, in some cases even above 50 MPa. The
tested mixtures exhibit several different phenomena:

 two-component mixtures (BFS + SiF) set considerably longer than standard cements according
to the above standards expressed by the Vicat method (STN EN 196-3), depending on the type
of mixture, the initial setting time is generally significantly over 24 h;
 the development of setting after addition of 1 to 4 % of clinker, or Portland cement, or 2 to 4 %
of sulphates, or mixtures thereof, accelerates the setting within few hours and the final setting
time is so extremely rapid that it occurs within a few minutes after the initial setting time (IST),
meaning that the setting time interval (SI) in min., which is the difference between the final
setting time (FST) and the initial setting time according to

SI = IST - FST (2)

 is very short. The mathematical expression of the setting time curve obtained from Vicat test as
the setting rate, which is the so-called setting coefficient (SC) as the ratio of the initial setting
time (IST) to the setting period – expressed as the final setting time according to

SC = IST / FST (3)

 is approaching the value 1, with this value being 0.5 to 0.8 for standard cements. At PCLA, the
individual values have ranged from 0.80 to 0.99, with the automatic Vicat apparatus having
recorded several times values close to 1, which meant that the termination of the setting
occurred in a discontinued manner – virtually by a step change from a semi-liquid - plastic state
to the solid state within a few minutes. However, the addition of the above mentioned activators
is sufficient at a much lower level – as little as 0.25 % and more significantly 0.5 % of CEM I
42.5 R clinker/cement reduces the IST and FST to a standard setting period of several hours;

 the mixtures prepared in this way achieve a higher index of long-term strength development
(ILTSD) after 120, 180 and 365 days of setting (130 to 170 %, exceptionally more) than standard
cements. The qualitative ILTSD indicator for the compressive strength of cement for a setting
period of 120, 180 to 365 days, is the ratio of CS 120 days to CS 28 days, expressed as
ILTSD120, or the ratio of CS 180 to CS 28 days expressed as % ILTSD180, ILTSD365 is similar:

ILTSD = CSt / CS28 x 100 % (4)

 In literature, this indicator is also called relative strength (EN 196-1, 2015);

 the mixtures prepared in this way, in conjunction already with the low clinker addition, reach
higher heats of hydration after 7 days (HH7), but mainly after 14 days (HH14), possibly after 21
days of hardening and in a later period than the BFS itself, or the same BFS with the same
addition of the same clinker;
 the base mixture prepared in this way achieves high plasticity, the rheological properties are
significantly shifted, towards increased shear stress, by 30 – 50 % compared to pure CEM I and
it has significantly improved adhesive effects (as compared to pure cement binder) both as a
two-component and as a three-component, or four-component, mixture, with its adhesive
effects, tested according to (Hlaváč 1981, STN 72 2446 1968), improving significantly.

The hardening of this mixture with standard sand on 40 x 40 x 160 mm beams according to (EN 197-1,
2005) takes place during the first 7 days, first in humid storage at 20 ± 1 ° C and a relative humidity of
about 90 %, in the next period the increase in hardening already on the beams stored in an aqueous
environment is 20 ± 1 °C.
 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

2. EXPERIMENTAL

Granulated blast-furnace slag from different origins and silica fume were used as besed components for
the preparation of S-S binders. Portland cement CEM I 42.5 R /Portland clinker, natural gypsum were
used as activators. The isothermal calorimeter investigation was performed using an eight-channel TAM
(Thermal Activity Monitoring) instrument using glass ampoules. In this chapter the emphasis of the main
part has been put not only on the physicochemical properties of the hydrated S-S binder, but mainly on
monitoring the development of the exothermic reaction – even over a longer period of time of 14 – 21
days (Ježo 2010). Samples were cured under standard conditions. Microstructures of cement pastes
after hydration and 28 days storing were studied by SEM (TESLA BS 300) to find a evidence of
crystallohydrate presence and their morphology.

3. RESULTS AND DISCUSSION

By increasing the SiF content above 5 and more % to the BFS, we reach an area outside the quantity
in CEM III/C cement, permitted by the standard (STN EN 197 - Cement. Part 1 2005); with the content
increasing to 10 % – 20 % we get hypothetical cement with the working name "Modified Blast-Furnace
Cement" or "Slag-silicate binder LADCEMENT". It has not been possible to state here all detailed
results, but they have been published in 70 tables in (Patent Nr. 288323).

The S-S resembles to a certain degree the geopolymer cement, which has been elaborated on in detail
by (Škvára 2007) and Tomková (Tomková 2004) and by others (Davidovits 1988, Odler 2000) globally,
but the essential difference is that, to be “activated”, it does not need expensive activators such as
NaOH, KOH, water glass, soda, potash or energetically modified kaolin – metakaolin. From Figure 1.,
the microstructure of the S-S binder seems to be equally compact of the inner-type as compared to the
equally hydrated sample of 80% BFS + 20% C3S (Ježo 2010) which is more of the outer type. Such a
microstructure achieves CS comparable to that of geopolymer cements over a long period of 0.5 – 1
year.

A micrograph from an electron microscope (Figure 1.): the samples – hydrated pastes, were stored for
28 days in standard water storage and after 1 year of subsequent free storage in the laboratory the
microstructure was observed. The left picture shows a BFS microstructure with the addition of 20 % of
SiF, the right picture shows the microstructure with the addition of 20 % of C3S (Ježo 2010). Typical of
the BFS sample with added C3S is the microstructure of a network made up of a porous C-S-H gel and
acicular-lamellar crystals of the hydration products covering the slag particles. In the case of the BFS
sample with SiF addition, the microstructure of the matrix is very compact, it is characterized by a very
finely grained microstructure of SiO2 particles and internal pores at the level of the size of these particles
and it seems to be comparable to the structure of geopolymers (Odler 2000).

a) 20 % SiF in BFS, magnified 20,000 x b) 20 % C3S in BFS, magnified 20,000 x

Figure 1. Comparison of the microstructure of BFS samples with the addition of 20 % of SiF
and 20 % C3S of at different magnification

3.1 Calorimetric measurements

Figure 2. shows a comparison of the heat flow of hydration of 3 types of BFS, ground in the same way,
fraction 0 – 0.09 mm, all three meet the requirements (STN EN 197 - Cement. Part 1 2005, STN EN
 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

15167-1 2006), but only BFS Třinec is highly active (SAMBFS = 460 m2 kg-1, tmax HH = 1698 min, Pmax HH
= 1.59 mW, HH7 = 70.8 J g-1), while the other two BFS originating from US Steel Košice (HH7 = 39.3 J
g-1, SAMBFS = 280 m2 kg-1) and from Munich (HH7 = 31.7 J g-1, SAMBFS = 268 m2 kg-1) are less active
and less suitable for the S-S binder, but usable with an activator.

Figure 2. Comparison of the heat flow of hydration of 3 types of BFS without activators

Figure 3. shows an overview of the exothermic hydration reaction of the hydration of a medium-active
BFS originating from TŽ, Třinec – (SAMBFS = 390 m2 kg-1, HH7 = 62.7 J g-1, HH14 = 86.4 J g-1, tmax HH
= 5132 min, Pmax HH 1.12 mW), the second hydration curve (HH7 = 46.2 J g-1, HH14 = 87.0 J g-1, tmax HT
= 9745 min, Pmax HH 1.00 mW) represents a mixture of 90 % BFS + 10 % SiF – an easily interpreted
graphic illustration of the shift of the reaction rate to over 7 days due to the addition of SiF, the lower,
third curve shows a mixture of 80 % BFS + 20 % SiF (HH7 = 38.5 J g-1, HH14 = 97.6 J g-1, tmax HH =
11650 min, Pmax HH = 0.86 mW).

Figure 3. Overview of the heat flow of hydration of medium-active BFS from Třinecké železárny
(Czechia), HH7 = 62.7 J g-1

Figure 4. shows a similar example – the first addition to the highly active BFS Košice (HH7 = 37.1 J g-1)
with particle size below 0.090 mm, SAMBFS = 452 m2 kg-1, was 20 % SiF (mixture designation: 8/2 KE)
and, subsequently after homogenization, 2 % of standard finely ground clinker (designated as 8/2 KE +
2 % clinker) was added to the mixture, i.e. the CK III/C20/2 S-S binder was created.
 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

Figure 4. Comparison of the heat flow of hydration of the pure BFS KE, 80 % BFS + 20 % SiF
and 98 % BFS 2 % clinker

3.1.1 Influence SiF and CEM I 42.5 R addition on hydration of lower active
The increase in HH indicates the control mechanism of CS growth by means of a chemical reaction
rather than its physical nature due to a change in rheology and normal consistency of S-S binders
(a seeming reduction in the water coefficient, which however has always been in line with the
requirements (STN EN 196-1 2006).

Figure 5 shows an overview of 1 type of the lower active BFS, with lower glassiness – originating from
US Steel Košice, SAMBFS = 290 m2/kg, in the mixtures B, C and these mixtures have been activated
by a 2 % addition of standard CEM I 42.5 R Portland cement (The designation is CEM III/C 10/2, CEM
III/C20/2).

Table 1. The influence of the 2 % of CEM I 42.5 R on the hydration of BFS with addition of SiF to
HH28

Time /d
Type of samples
1 7 14 28
BFS KE 100 % (A) 10.88 16.33 62.00 98.69
98 % BFS KE + 2 % CEM I 42.5R (B) 21.27 51.56 67.51 90.17
90 % BFS + 10 % SiF (C) 11.48 20.72 32.59 111.66
80 % BFS + 20 % SiF (D) 12.00 19.69 28.79 51.25
98 % (90BFS+10SiF) + 2 % CEM I 42.5R (E) 19.23 67.05 94.32 134.16
98 % (80BFS+20SiF) + 2 % CEM I 42.5R (F) 20.69 80.37 119.44 179.14
This addition of cement has greatly shifted the hydration kinetics to a favourable setting period of the
mixture to a level of few hours. The BFS used here is not suitable for the Ladcement binder itself, only
with SiF; in this case, at least one third component at a level of 0.5 – 2 % based on clinker or Portland
cement or the fourth activating component has to be added.

Figure 5. Comparison of the heat flow of hydration of the BFS itself, with SiF and CEM I 42.5 R
 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

3.1.2 The results of the measurement of CS and Vicat characteristics of the mixture of 90 %
BFS and 10 % SiF
In this example, 7 kg of a base mixture of 90 % BFS and 10 % SiF was homogenized by joint grinding
in a laboratory mill for 1 hour as standard, and then small amounts of activators were added to this
mixture and homogenized as shown in Table 2.

Table 2. Strength characteristics of a mixture of 90 % of BFS and 10 % of SiF with addition of

clinker and natural gypsum

Samples Component /% Mechanical strength in days /MPa VICAT /min

ILTSD90
BFS SiF CLIN GYPS. CS2 CS7 BS28 CS28 CS90 IST FST
Standard 90 10 - - 2.4 9.9 2.3 13.1 13.4 1260 2970 102.3
Sample 1 90 10 0.25 - 3.1 10.0 1.8 16.7 30.5 360 430 182.6
Sample 2 90 10 0.5 - 3.9 11.6 8.5 31.0 43.7 285 355 141.0
Sample 3 90 10 1 - 4.4 9.3 6.4 17.8 19.3 225 250 108.4
Sample 4 90 10 2 - 3.8 8.9 5.8 13.4 17.3 365 450 129.1
Sample 5 90 10 1 1 4.6 11.3 7.2 19.4 24.3 270 335 125.2
Sample 6 90 10 2 2 5.0 9.6 5.5 14.8 19.2 145 260 129.7
Sample 7 90 10 - 2 3.8 14.9 3.1 19.8 20.5 400 500 103.5
The CS results show that while the actual mixture without activators does not exhibit significant CS, a
small addition of 0.25 % of clinker increases the CS, be it only slightly, but 0.5 % of clinker increases
them by 1.5 MPa for CS_2, similarly by 1.7 MPa for CS_7, but more than 2 times for CS_28, where they
reached as much as 31 MPa. A further increase of activators at a low level of 2 – 4 % only results in an
increase in the initial CS_2, in part CS_7, but CS_28 is increased by them only slightly compared to the
standard.

3.1.3 The results of measuring the strength characteristics of the mixture (89 % BFS + 1 %
CEM I) and 10% SiF
For comparison with the previous example in Table 2, Table 3 shows the increase in strengths of a
mixture of 89 % BFS + 1 % of CEM I 42.5 R Portland cement and 10 % SiF (Sample 1). This mixture
was subsequently enriched with a further small addition of clinker and natural gypsum and their mixture
(Sample 2-6) in very low quantities at the level of a few %, which is sufficient for considerably higher CS
than in the previous example already after two but more significantly after 7 days of hardening: 11 to 18
MPa, but especially after 28 days of hardening 27.7 MPa to 38.2 MPa and CS_90 as much as 41 to
50.1 MPa.

Table 3. Strength characteristics of a mixture of 89 % of BFS, 1 % of CEM I 42.5 R and 10 % of

SiF with a subsequent small addition of clinker and natural gypsum

Components /% Mechanical strength in days /MPa

Sample No. CEM I ILTSD90
BFS SiF CLINKER GYPS. CS2 BS7 CS7 BS28 CS28 CS90
42.5R
Standard 90 - 10 - - 2.4 2.5 9.9 2.3 13.1 13.4 102.3
Sample 1 89 1 10 - - 4.3 5.3 12.6 6.7 27.7 41.0 148.0
Sample 2 88 1 10 1 - 4.5 4.8 9.9 6.0 15.9 23.3 146.5
Sample 3 87 1 10 2 - 5.0 4.1 9.7 5.7 15.7 19.5 124.2
Sample 4 87 1 10 1 1 5.3 5.1 11.5 6.9 19.1 23.7 124.1
Sample 5 87 1 10 2 2 4.9 4.3 9.8 5.1 13.6 16.7 122.8
Sample 6 87 1 10 - 2 3.4 5.8 18.4 9.2 38.2 50.1 131.2

3.1.4 The characteristics of a mixture of 80 % of BFS and 20 % of SiF with further addition of
activators
Sample "a" designated as the standard without any addition of clinker or other activator meets the
physical and mechanical requirements of a less demanding standard. Similarly, the samples no. 1 to 5
significantly exceed the standard requirement CS = 22.5 MPa and 32.5 MPa according to (STN EN 196-
 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

1) and they are well below the 220 J g-1 limit set for the heat of hydration. The samples no. 2 – 5 also
meet the requirement CS_7 > 12 MPa for cement of the strength type 32.5 L – LH.

Noteworthy are CS_90, where CEM III/C20/0 as well as CEM III/C20/0.5 (the standard is without clinker
and sample 1 with the addition of only 0.5 % of clinker) reached high values above 64 MPa, which is
ILTSD90 = 239 % and 240.1 %.

Table 4. Strength characteristics of a mixture of 80 % of BFS and 20 % of SiF with a small

addition of clinker and natural gypsum

Components /% Compressive strength in days /MPa VICAT /min ILTSD90

Sample No.
BFS SiF CL. GYPS. CS2 CS7 CS28 CS90 IST FST /%

Standard 80 20 0.0 1.1 27.1 64.9 2.550 4.130 239.0

Sample 1 80 20 0.5 0.2 6.1 26.9 64.6 880 1.130 240.1
Sample 2 80 20 1 2.2 13.5 40.1 47.5 420 770 118.4
Sample 3 80 20 2 3.6 12.2 34.8 54.9 330 405 157.8
Sample 4 80 20 1 1 3.2 15.1 41.2 47.1 360 550 114.3
Sample 5 80 20 2 2 4.7 15.5 36.5 37.9 300 330 103.8
Sample 6 80 20 2 0.0 0.8 6.5 23.9 1.695 1.995 3.677

3.1.5 The results of measuring the strength and Vicat characteristics of a mixture of higher
active BFS with 10-40% SiF
Table 5. shows an increase in the CS of another BFS, from Třinecké železárny a.s. (SS 430 m2 kg-1,
SAMBFS = 405 m2 kg-1) in conjunction with 10 – 40 % SiF over a long period of 180 days. While the
BFS alone, although sufficiently highly active, exhibits relatively high CS_7 at 9.3 MPa, later CS do not
increase anymore. Conversely, mixtures with a 10 and 20 % addition of SiF, although they have an
extended IST and FST, grow in CS primarily within a time period of 120 and 180 days.

From the heat flow of hydration in Figure 6., one can see a significant shift in hydration kinetics and the
development of HH7 heat of hydration of these mixtures from Table 5 shows the highest increase in
HH7 for the 30 % SiF mixture (75.3 J g-1), which is an increase by 121 % compared to the addition of
10 % of SiF (62,2 J g-1), 121 %, but the increase in HH7 for the addition of 20% of SiF (71 J g-1) is
sufficiently large – 114 % with a trend of its long-term growth later on, which has been fully confirmed
by the long-term development of the strengths.

Table 5. Strength characteristics of mixture of BFS and 10 – 40 % of SiF

Components
Sample Compressive strength and in days /MPa VICAT /min ILTSD /%
/%
No.
BFS SiF CS7 CS28 CS90 CS180 IST FST ILTSD90 ILTSD180

Sample 1 100 0 9.3 14.6 16.8 18.5 510 1.460 115 127
Sample 2 90 10 13.4 28.7 46.6 48.9 970 4.320 162 170
Sample 3 80 20 10.4 28.5 55.7 61.3 3.580 5.760 196 215
Sample 4 70 30 1.9 21.7 51.1 59.5 - 8.000 235 274
Sample 5 60 40 0.6 2.7 27.4 40.0 - 9.000 1.015 1.481
 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

Figure 6. Comparison of the flow of mixtures of BFS with a 10 – 50 % addition of SiF to the BFS

3.1.6 The results of the strength characteristics, Vicat characteristic and exothermic
characteristics of the mixture of higher active BFS with the addition of 10 – 50 % of SiF
in the presence of a low content of the activator
Table 6. contains the measured results for CS from BFS originating from US Steel Košice, SS 445 m2
kg-1, SAMBFS = 425 m2 kg-1, showing a positive increase in strengths and acceleration of the setting of
a mixture of 98 % of BFS enriched with 2 % of standard Portland cement CEM I 42.5 R in mixtures with
the addition of 10 to 50 % of SiF, which is sufficient for standard high CS as early as after 7 days of
hardening – 15 to 20 MPa, but especially after 28 days of hardening 24 – 38 MPa, with the CS further
increasing in the period of 120 to 180 days and exceeds 50 MPa. The IST is only adequate for the cases
of addition of 10 – 30 % of SiF to the mixture of the BFS and the activator – the cement.

Table 6. Strength characteristics of a mixture of BFS and 10 – 50 % SiF with a small addition of
CEM I

Composition /% Compressive strength /MPa VICAT /min

Sample
CEM I Addition ILTSD180 HH7
No. SiF BFS CS2 CS7 CS28 CS180 IST FST
42.5 R of water
Sample 1 0 100 0 225 - 8.1 9.6 17.7 min min 134.5 -
Sample 2 10 88 2 225 6.6 14.7 23.8 35.8 - - 150 62.2
Sample 3 20 78 2 225 2.9 20 37.9 53.5 205 250 141 71.0
Sample 4 30 68 2 275 1.5 11.3 34.9 62.2 205 215 178 75.3
Sample 5 40 58 2 325 - 5.0 26.9 50.1 480 490 186 24.6
Sample 6 50 48 2 325 - 1.5 22.0 32.5 - - 148 23.8

3.1.7 The results of measuring the HH of a mixture of the lower active BFS with the addition of
5 – 20 % of SiF and with the addition of 3 % of clinker
Table 7. shows a record of the measurement of the long-term heat flow of hydration within 21 days,
which documents a contribution of SiF in the range of 5 – 20 % to the lower active BFS in the grinding
variants A) = SS 400 m2 kg-1, SAMBFS = 298 m2 kg-1 (the first 6 samples) and the variant B) = SS 510
m2 kg-1, SAMBFS = 380 m2 kg-1 (the last 2 samples) at a constant addition of 3 % of clinker. While the
quantity of 5 % of SiF does not have a positive effect on HH7 and HH14, from 10 % onwards one can
see a significant increase – not yet in HH7 but – in HH14.

The impact of the addition of 3 % of clinker to two BFSs of different fineness (the first one ground to SS
= 400 m2 kg-1, the second one ground to MP 510 m2 kg-1) with addition of SiF to HH21 days.
 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

Table 7. Record of the measurement of the long-term heat flow of hydration within 21 days

Type of samples Time /d

1 7 14 21
BFS KE SS 400 8.23 19.38 50.06 68.36
BFS + 3 % clinker 14.93 49.99 64.51 74.78
BFS + 3 % CL+ 5% SiF 12.34 38.94 51.58 61.16
BFS + 3 % CL + 10% SiF 17.13 44.92 61.21 72.5
BFS + 3 % CL + 15% SiF 19.09 46.73 67.01 79.82
BFS + 3 % CL+ 20% SiF 18.49 46.20 71.09 87.68
BFS MP 510 + 3 % CL + 10% SiF 21.87 55.49 78.87 97.7
BFS SS 510 + 3 % CL + 15%SiF 16.99 44.41 68.52 86.41

In this context, composite cements have clearly manifested positive results in terms of a significantly
higher technical indicator, which is the achieved strength of the cement in the respective period in
MPa/1% of clinker in the given cement, the so-called "MIXTURE-CLINKER STRENGTH FACTOR" of
the cement/binder in general (MCSFCS, abbrev. FS)

MCSFCS = CS of the cement/CLINKER CONTENT in the cement = FS (5)

This technical indicator has a significant informative value in determining the effectiveness of clinker
utilization in the cement (and thus the effective use of the clinker factor and its strength potential) when
we monitor the achieved CS of the cement over a rather long period of time of 28 days to 1 year, given
the amount of clinker used in this cement.

Table 8. A comparison of CS and MCSFCS (abbreviated FS) in Portland cement, different

composite cements, in a CEM III/C blast furnace cement and in a S-S binder (• CS measured
after 90 days)

Share of constituents CS in days/ MCSFCS in 2, 7, 28, 180 and 365 days

CS
Clinker Lime FA BFS SiF CS2 FS2 CS7 FS7 CS28 FS28 FS180 CS1Y FS1Y
180
MPa/ MPa/ MPa MPa MPa
% % % % % MPa MPa MPa MPa MPa
1% 1% /1% /1% / 1%
93 2 - - - 42.2 0.45 - - 71.8 0.76 - - 86.0 0.92
65 30 - - - 27.4 0.42 - - 49.6 0.70 49.8 0.76 50.6 0.78
65 - 30 - - 26.4 0.41 - - 58.1 0.89 76.8 1.18 83.3 1.28
47 - 50 - - 15.4 0.33 - - 41.7 0.89 67.0 1.42 79.1 1.68
27 20 - 50 - 4.2 0.16 13.2 0.49 31.4 1.16 43.5 1.61 47.3 1.75
27 20 50 - - 7.1 0.26 14.2 0.53 27.7 1.03 53.9 2.00 59.0 2.19
85 - - - 10 30.5 0.36 - - 71.1 0.84 77.8 0.92 80.1 0.94
10 - - 90 - - - 12.2 1.22 37.0 3.70 48.3 4.83 - -
15 - - 85 - - - 12.1 0.81 48.8 3.25 61.8 4.12 - -
• •
1 - - 89 10 5.3 5.3 12.6 12.6 27.7 27.7 41.0 41.0 - -
1 - - 79 20 2.2 2.2 13.5 13.5 40.1 40.1 47.5• 47.5• - -

E.g. for a 30 % use of FA in CEM I 52.5 R with a 95 % clinker content and 5 % content of the set
controlling agent the following holds for pure Portland cement:

MCSFCS-28 = 67.2 MPa/(100-5)% = 0.7 MPa/1% of clinker, but the following holds with 30% fly ash
(FA) substitute:

MCSFCS-28 = 58.1 MPa/(100 - 5 - 30)% = 0.9 MPa/1% of clinker, with the relation for 1 year being:

MCSFCS-1Y = 75.7 MPa/(100-5)% = 0.8 MPa/1% CL for Portland cement,

 15th International Congress on the Chemistry of Cement
Prague, Czech Republic, September 16–20, 2019

MCSFCS-1Y = 83.3 MPa/(100 - 5 - 30)% = 1.3 MPa/1% CL for CEM II/B-V cement, meaning that the
usability in CS of each % of clinker is 1.3/0.8 = 1.6 times higher in cement with a 30% clinker decrease
at the expense of a Pozzolan addition of FA in CS_1R.

Table 8. shows in several examples (for several cement types) an increase in the strength potential
expressed as FS in the achieved MPa/1% of clinker. Over a long period of 28 days or more, for
composite cements with declining clinker content, the mixture-clinker factor FS increases significantly
(the highest resulting value is that of CEM III/C blast furnace cement with 3.7 MPa/1% CL). While the
"usability of clinker" in Portland cement is more favourable in earlier CS_2, CS_7, the opposite is true
for long-term CS. The last 2 rows of Table 8 are noteworthy – the FS for the S-S binder CEM III/C10/1 is
more than 10 times higher than for Portland cement, as early as at CS_2 and CS_28 it the value is more
than 36 times higher (27.7/0.76 = 36.4). Similarly, for CEM III/C20/1, the FS increase for CS_2 is as
follows: 2.2/0.45 = 4.9 times higher, for CS_28 the value is as much as: a 40.1/0.76 = 52.6 times higher
FS as compared to Portland cement.

4. CONCLUSION

Cements with a lower clinker factor are considerably cheaper than the Portland cements produced and
sold so far (i.e., a shift of the share of additional constituents towards an increase in the content of
cheaper BFS, limestone and power station fly ash at the expense of a more expensive and more energy-
intensive clinker), even though they require some refinement of the grinding process. However, the
clinker production costs account for as much as about 70 % and the costs of grinding it to cement
account for only about 30 % of the production costs of conventional Portland cements.
In the field of S-S binders, the economic aspect is as follows:
Because 1 tonne of SiF is several times more expensive than clinker, when using 10 – 20 % of SiF, 79
– 89 % of BFS and 1 % of clinker 1 tonne of S-S binder may be more economic than the cements
produced so far, when the high transport costs for BFS and SiF are not included in calculation of the
price, i.e. when the production takes place in the place of the deposits or near the source of one or both
constituents.
Generally, this new binder will become very attractive in the industry in the near or further future, when
global warming melts the bulk of the earth's glaciers, the sea level begins to rise noticeably, e. g. only
by 1 meter, so that 1 tonne of CO2 will cost a clinker manufacturer not 10 – 20 EUR/tonne, but 100 –
500 EUR/tonne. Only then, minimization of the production of Portland cements and an effective use of
Portland clinker, rather than saving time (the current use of Portland cements), will become a problem
for society as a whole.

5. ACKNOWLEDGEMENTS

The work was supported financially by Cement Plant PLCA Ladce.

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