Available online at www.sciencedirect.

com

ScienceDirect
Procedia Engineering 172 (2017) 1015 – 1022

Modern Building Materials, Structures and Techniques, MBMST 2016

The influence of biomass fly ash on the plasticizing effects in

cement pastes
Gintautas Skripkiūnasa, Mindaugas Macijauskasb, *, Džigita Nagrockienėc, Aurelijus 0F

Daugėlad
a,b,c,d
Department of Building Materials and Products, Faculty of Civil Engineering, Vilnius Gediminas Technical University, Saulėtekio al. 11,
LT-10223 Vilnius, Lithuania

Abstract

The aim of this work is to determine the impact of biomass fly ash (BM-FA) on the plasticizing effects in cement pastes. The
rheological properties of the cement pastes have been determined using rotational viscometer with coaxial cylinders Rheotest
RN4.1. These tests, using rotational viscometer, have been conducted by making the assessment of cement paste flow curves,
using Bingham rheological model. The rheological properties (yield stress, viscosity and thixotropy) of cement paste were
determined at different times after paste mixing: 0 min, 30 min, 60 min, 90 min and 120 min. The cement pastes with same W/C
ratio equal 0.35 were tested. 0 %, 5 %, 10 %, 20 % and 30 % of cement were replaced by BM-FA. The rheological behavior of
the cement pastes was also studied and compared to that of a reference BM-FA free production in order to evaluate the effect of
BM-FA addition on rheological properties. Results showed that having replaced 10 % of cement with BM-FA the paste exhibits
better rheological properties: not only lower yield stress but also lower viscosity from mixing until 120 min after. Adequate
amount of BM-FA (10 %, in this case) not only improves rheological properties but also helps retaining plasticizing effect for the
period of 120 min, which is important in long distance concrete mixtures transportation. It was observed that having replaced up
to 10 % of cement with BM-FA thixotropy was also improved and the fresh concrete mixtures produced can be transported,
molded, consolidated, and finished within 90 minutes from mixing without losing good workability and rigidity.

©
©2017
2016Published by Elsevier
The Authors. Ltd. This
Published is an openLtd.
by Elsevier access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of MBMST 2016.
Peer-review under responsibility of the organizing committee of MBMST 2016
Keywords: biomass fly ash; cement paste; yield stress; viscosity; rheological properties, thixotropy.

* Corresponding author. Tel.: +370 5 274 5219; fax: +370 5 270 0112.
E-mail address: mindaugas.macijauskas@vgtu.lt

1877-7058 © 2017 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of MBMST 2016
doi:10.1016/j.proeng.2017.02.152
1016 Gintautas Skripkiūnas et al. / Procedia Engineering 172 (2017) 1015 – 1022

1. Introduction

Environmental concerns and economic pressures are amongst the driving forces of today’s industrial
developments. Thus, considerable researches have been conducted worldwide on the use of waste materials to avert
the increase of threats to the environment and to streamline present waste disposal and recycling methods by making
them more affordable [1].
The production of the most common cement binder – Ordinary Portland Cement (OPC) – is related to the
extremely high input of fuel and the great emission of CO2 into environment. The emission of CO2 by the industrial
production of cement makes 5 % – 7 % of total CO2 emission. Until relatively recently, the use of additives and
substitutes to OPC has been one of the most successful ways to decrease the CO 2 emissions generated by cement and
concrete producers, and amongst those the so called “industrial wastes” have got a wide attention [2-9].
Therefore, we have witnessed recent intensification of research into composite cement binders and their
concretes. A certain proportion of OPC in these concretes could be replaced by other active additives (i.e.: silica
fume, slag, fly ash, natural pozzolans), particularly by the wastes. Waste with pozzolana properties, which can
improve the resistance of cement products to alkaline and sulphate corrosion, modify their hardening process,
structure and increase the strength, etc. is particularly attractive [10]. One of the most promising types of waste is
biomass fly ash (BM-FA).
The rapidly increasing amount of BM-FA produced all over the world leads to the need to recycle, not only due to
the rising cost of the landfill disposal which, in turn, is reflected on the cost of the energy produced, but also as a
consequence of the “zero-waste” objective which is often suggested as the final goal of all future human activities
[11]. The use of BM-FA in cements, mortars or concretes is presently under study because their recycling in the
production of cement based materials could have a beneficial impact on environment provided that it is possible to
demonstrate that the resulting products have good mechanical properties, long durability and low pollution release of
hazardous elements.
Based on the physical, chemical and morphological properties, it is reported that BM-FA, an industrial by-product
of thermal power plants, has a substantial potential for use as a pozzolanic mineral additive and/or as an
activator/binder in cement-based materials [12-16].
Fresh concrete is a concentrated suspension of particulate materials of widely differing densities, particle sizes,
and chemical compositions in a solution of lime and other components. Because concrete must be mixed, placed
(i.e.: frequently in a heavily reinforced formwork), molded, consolidated, and finished, it is necessary that in most
cases a level of fluidity, generally termed workability, be maintained. This is determined by the rheological
properties of the system, which are, in turn, influenced by all the components. Control of workability is one of the
objectives of mixture proportioning.
Water-reducing admixtures and superplasticizers can be used to significantly increase the workability and
consistency, or reduce the water demand of concrete, and are widely used in concrete production today.
Supplementary cementing materials (SCMs) can also have a significant impact on the workability, consistency, and
water demand of the concrete. The effect depends on the type of SCMs and the level of replacement, among other
factors. Therefore, it is essential to understand the role of BM-FA in the rheology of fresh concrete to fully exploit
the potential of BM-FA for improving concrete.
According to Owens [17], the major factor influencing the effects of ash on the workability of concrete is the
proportion of coarse material (>45 μm) in the ash. Owens has shown that, for example, substitution of 50 % of the
material >45 μm has no effect on the water requirement.
Stuart et. al. [18] studied the effect of high-range water-reducing admixtures and fly ashes on the water
requirements of various mortars. The results showed that the fly ashes themselves were effective in reducing water
content but differed considerably in their effectiveness as water-reducing admixtures.
Following up on Stuart’s results, Helmuth [19] suggested that the water reduction caused by the fly ash was the
result of an absorption and dispersion process as much like that of organic water-reducing admixtures.
Rajamma et. al. [1] studied the impact of BM-FA on fresh and hardened state properties of cement based
materials. The results showed that, in general, the water demand of BM-FA/OPC blended cement pastes increases
with the content of ash. Up to 10 % BM-FA the influence in the consistency of cement mortars is not visible, but
 Gintautas Skripkiūnas et al. / Procedia Engineering 172 (2017) 1015 – 1022 1017

when substitution dosage of ash increase above 20 % the water demand also increases significantly. These results are
in agreement with the findings of earlier researchers on wood ashes from other sources, such as saw dust [20-22].
The aim of this work is to determine the impact of biomass fly ash (BM-FA) on the plasticizing effects in cement
pastes. The cement pastes with same W/C ratio equal 0.35 were tested. 0 %, 5 %, 10 %, 20 % and 30 % of cement
were replaced by BM-FA. The rheological behavior of the cement pastes was also studied and compared to that of a
reference BM-FA free production in order to evaluate the effect of BM-FA addition on rheological properties.

2. Research methodology and materials used

Portland cement CEM I R (PC R) according to EN 197-1 (strength class 42.5 R), produced by JSC Akmenės
Cementas was used in the investigation. Clinker mineral composition (according Bogue calculation) was: C 3S – 61.0
%, C2S – 13.5 %, C3A – 8.5 %, C4AF – 10.5 %, SO3 – 3.10 %, LOI – 1.43 %. Particle density is 3.11 g/cm3 and dry
bulk density is 1.22 g/cm3. The average size of particle is 15.05 μm, 50 % particles are smaller than 9.94 μm. The
codes of cement used and its physical properties are given in Table 1.
Chemical composition of biomass fly ash (BM-FA) used for investigation was: SiO2 – 51.8 %, Al2O3 – 1.93 %,
Fe2O3 – 1.67 %, CaO – 26.5 %, K2O – 6.87 %, MgO – 1.91 %, P2O5 – 3.19 %, SO3 – 3.74 %, Na2O – 0.176 %, MnO
– 0.834 %, Cl – 0.670 %. The average size of particle is 69.33 μm, 50 % particles are smaller than 23.97 μm. BM-
FA specific surface area is 3083 cm2/g.
Superplasticizer Sika D187 (SP) based on synthetic polycarboxylate ester (PCE) was used (consistency – liquid,
conc. of active material in solution – 18%, density – 1.08 g/cm3, max. chloride content < 0.10 %, max. alkali content
< 0.1 %). Chemical admixture content in cement paste was constant – 0.75 % of the cement weight.
The particle size distribution of cement and biomass fly ash and their granulometry curves are presented in the
Fig. 1. These parameters were determined using Cilas 1090 Liquid (France).

Table 1. Physical properties of cement (according EN 197-1).

Compressive strength, Setting time,
Fineness
Type of MPa min Standard consistence (water content in
Code
cement %) Blaine, > 90μm,
7 days 28 days initial final
cm2/g %
CEM I 42.5 R PC R 28.9 54.6 150 200 25.4 3560 1.1

Fig. 1. Particle size distribution of cement (PC R) and biomass fly ash (FA-BM) and their granulometry curves.

Cement paste was mixed in a hand mixer according to EN 196-1. The mixing procedure was as follows: cement
and 3/4 of required water were mixed for 2 min at low speed, after that the remaining water and SP were added in
and cement paste was mixed further for 1 min at high speed.
1018 Gintautas Skripkiūnas et al. / Procedia Engineering 172 (2017) 1015 – 1022

The rheological properties of cement paste were tested using rotational viscometer with coaxial cylinders
Rheotest RN4.1 with gap between cylinders of 1.48 mm. The cylinder measuring system consists of the measuring
cup (assembled) (1) with coupling (3) and cylinder rotor (2). The dimensions of testing cylinders are presented in
the Fig. 2.
The shear rates used in the test are presented in the Fig. 3.
The cement paste is poured into a measuring cup (1), which is fixed non-movably into the equipment stand.
Inside the measuring cup the cylinder rotor (2) can rotate. Because of the intrinsic friction of the layers of the
cement paste (4) appearing between the measuring cup (1) and the rotating cylinder rotor (2) positioned in the
measuring cup and connected to a measuring scale; the cylinder rotor (2) makes a turn and the data displayed on the
measuring scale changes.

Fig. 2. Principle schema of testing cylinders.

Fig. 3. Shear rates during testing vs. testing duration.

Rheological properties of cement paste were tested at different times after paste mixing: 0 min, 30 min, 60 min,
90 min and 120 min. The cement pastes with same W/C ratio equal 0.35 were tested. 0 %, 5 %, 10 %, 20 % and 30
% of cement were replaced by BM-FA. A test of rheology was carried out at temperature 20±2 °C.
The yield stress and viscosity of cement paste were calculated from flow curve (τ and ν curve) obtained after the
test with rotational viscometer. The flow curve of cement paste was analyzed adopting the Bingham rheological
model using linear approximation of experimental results up to 100 s -1 shear rate when flow curve of cement paste is
linear character. The EXEL computer application was used for this purpose (Fig. 4).
The yield stress of cement paste (τ0) and viscosity (η) values were obtained from linear equation (Bingham
rheological model):

τ = τ0 + η·ν,
 Gintautas Skripkiūnas et al. / Procedia Engineering 172 (2017) 1015 – 1022 1019

where: τ – shear stress, Pa;

τ0 – yield stress of cement paste, Pa;
η – viscosity of cement paste, Pa·s;
ν – shear rate, s-1.

a) b)

Fig. 4. Calculation of (a) yield stress, viscosity and (b) thixotropy of cement paste from flow curve.

The thixotropy of cement paste was calculated from flow curve of cement paste obtained after testing in 300 s-1
shear rate (Fig. 4). The thixotropy value was calculated by the reduction of shear stress during the constant shear
rate equal 300 s-1 by the equation:

T = (τ1 – τ2) / τ1,

where: τ1 – shear stress at 300 s-1 before retention during testing, Pa;
τ2 – shear stress at 300 s-1 after retention during testing, Pa.

3. Results of experimental research

3.1. Flow behaviour of cement pastes

From the determined flow curves (see Fig. 5a and b), 5 or 90 minutes after the start of mixing, we can see that
cement PC R pastes with BM-FA and without it have different rheological properties.

a) b)

Fig. 5. Cement PC R pastes flow curves (shear stress dependency on shear rate) (a) 5 min and (b) 90 min after the mixing of the pastes.
1020 Gintautas Skripkiūnas et al. / Procedia Engineering 172 (2017) 1015 – 1022

From Fig. 5a we can see that having mixed into the PC R paste some plasticising admixture (superplasticizer SP
– 0.75 % of cement mass, in this case), the rheological properties of the paste improve: while the shear rate is
improving from 0 to 100 s-1, lesser shear stress is observed, compared to cement paste without SP. Seeking to
determine the impact of BM-FA on plasticised paste rheological properties, we received the following results:
having replaced 5 %, 20 % or 30 % of cement with BM-FA, giving increasing shear rate from 0 to 100 s-1,
respectively bigger shear stress was observed, compared to paste without BM-FA. With a notable exception: having
added 10 % of BM-FA, the opposite effect was observed – given increasing shear rate from 0 to 100 s-1, shear stress
is lesser compared to cement PC R paste without BM-FA.
From Fig. 5b we can see that even after 90 min from the mixing of the pastes, having 10 % of cement replaced by
BM-FA rheological properties did not change much compared to rheological properties of cement paste 5 min after
the start of mixing. In addition to that, as the shear rate increases from 0 to 100 s -1, pastes shear stresses are lesser
compared cement pastes with 5 %, 20 %, 30 % of BM-FA or without them. Thus, we can conclude that the 10 % of
BM-FA, given the same contents (V/C = 0.35), retain the prescribed paste plasticizing effect from the mixing until
90 minutes after.

3.2. Yield stresses and viscosities of cement pastes

a) b)

Fig. 6. Cement PC R pastes (a) yield stresses and (b) viscosities change within 120 min duration.

From Fig. 6a we can see that in cement PC R paste without BM-FA yield stress remains constant from the start of
mixing to until 60 min after. However, from 60 min margin onwards intensive yield stress increase was observed.
Having replaced 5 % or 30 % of cement with BM-FA cement paste yield stress increase marginally from the start of
mixing to until 90 min after. From 90 min onwards intensive yield stress increase is evident.
From Fig. 6a it is also evident that having replaced 10 % or 20 % of cement with BM-FA, the yield stress of
cement paste remains constant from the start of mixing until 90 min after. From 90 min marginal yield stress
increase is observed. Notably, having changed 10 % of cement by BM-FA we get significantly lower yield stress
measurements (8.03-9.43 Pa) compared to those of cement PC R pastes with BM-FA. Respectively: 5 % – 13.70-
43.10 Pa, 20 % – 13.30-17.10 Pa, 30 % – 14.70-31.30 Pa, or without them – 11.10-28.10 Pa, within 2 hour period
from the start of mixing.
From Fig. 6b we can see that viscosity of cement PC R paste with BM-FA (5 % of cement being replaced by
BM-FA) and without them gradually increases from the start of mixing until 60 min after. From 60 min onwards
intensive increase of viscosity is observed. Having replaced 20 % or 30 % of cement with BM-FA viscosity of
cement paste gradually increases from mixing until 90 min after. From 90 min margin onwards intensive increase of
viscosity is observed. However, having replaced 10 % of cement with BM-FA viscosity remains the same from
mixing until 60 min after. From 60 min onwards marginal increase is observed. In addition to that significantly
lesser viscosity of the paste was determined (0.44-0.65 Pa·s) compared to cement pastes with BM-FA respectively:
 Gintautas Skripkiūnas et al. / Procedia Engineering 172 (2017) 1015 – 1022 1021

5 % – 0.54-1.19 Pa·s, 20 % – 0.62-1.06 Pa·s, 30 % – 0.80-1.21 Pa·s, or without them – 0.44-1.07 Pa·s, within 2 hour
period after mixing.
In conclusion we can state that having replaced 10 % of cement with BM-FA the paste exhibits better rheological
properties: not only lower yield stress (see Fig. 6a) but also lower viscosity from mixing until 120 min after.
Adequate amount of BM-FA (10 %, in this case) not only improves rheological properties but also helps retaining
plasticizing effect for the period of 2 hours, which is important in long distance concrete mixtures transportation.

3.3. Thixotropy of cement pastes

Fig. 7. Cement PC R pastes thixotropy change within the period of 120 min.

In the case of many cementitious materials, a reversible evolution of the material rheological behaviour is often
noted during the dormant period of the hydration reaction: the apparent static yield stress continuously evolves. As
this evolution can be erased by a strong shearing of the paste and the material can be brought back to a reference
state, it is often described as thixotropy [23, 24, 25].
Cement PC R (specific surface area – 3560 cm2/g) paste thixotropy is largely influenced by BM-FA (specific
surface area – 3083 cm2/g) fineness, particle size distribution/granulometry (see Fig. 1) and amount in the paste.
From Fig. 7 we can see that having replaced 10 % of cement by BM-FA, thixotropy of cement paste for the
period of 2 hours from the start of the mixing of the paste changes marginally (0.11-0.14). Having replaced 20 % or
30 % – thixotropy of the paste is reduced respectively: 0.07-0.11, 0.02-0.09.
We can also observe that having increased the percentage of BM-FA in the paste to 10 %, thixotropy increases
within 60 min period. From 60 to 90 min – remains unchanged compared to thixotropy of the paste right at the start
of mixing. Thus, we can state that having replaced up to 10 % of cement with BM-FA thixotropy is improved and
the fresh concrete mixtures produced can be transported, molded, consolidated, and finished within 90 minutes from
mixing without losing good workability and rigidity.

4. Conclusions

Rheological properties of cement paste depend on biomass fly ash mineral composition, its fineness, particle size
distribution/granulometry and amount in the paste. In this work we determined:
1. With 10 % of cement replaced by biomass fly ash, the paste has better rheological properties: not only lower
yield stress (Fig. 6a), but also lower viscosity (Fig. 6b) in the period from mixing until 120 minutes after. 10 % of
biomass fly ash not only improves rheological properties, but also helps retain the plasticizing effect for the period
of 120 min, which is important in long distance concrete mixtures transportation.
2. Cement paste thixotropy is largely influenced by biomass fly ash (specific surface area – 3083 cm2/g) fineness,
particle size distribution/granulometry (see Fig. 1) and amount in the paste. Having replaced up to 10 % of cement
with biomass fly ash thixotropy is improved and the produced fresh concrete mixtures can be transported, molded,
consolidated, and finished within 90 minutes from mixing without loses in terms of workability and rigidity.
1022 Gintautas Skripkiūnas et al. / Procedia Engineering 172 (2017) 1015 – 1022

References

[1] R. Rajamma, L. Senff, M.J. Ribeiro, J.A. Labrincha, R.J. Ball, G.C. Allen, V.M. Ferreira, Biomass fly ash effect on fresh and hardened state
properties of cement based materials, Composites 77 (2015) 1–9.
[2] J. Duchesne, M.A. Berubet, Effect of supplementary cementing materials on the composition of cement hydration products, Adv Cem Bas
Mater 2 (1995) 43–52.
[3] M. A. Monteiro; F. Pereira, V.M. Ferreira, M. Dondi, J.A. Labrincha, Light weight aggregate based industrial wastes, Ind Ceram 25 (2005)
71–7.
[4] M. Dondi, M. Marsigli, B. Fabbri, Recycling of industrial and urban wastes in brick production: a review, Tile Brick Int 13 (1997) 302–8.
[5] M. Batayneh, I. Marie, I. Asi, Use of selected waste materials in concrete mixes, Waste Manag. 27 (2007) 1870–6.
[6] S. Antiohos, K. Maganari, S. Tsimas, Evaluation of blends of high and low calcium fly ashes for use as supplementary cementing materials,
Cem. Conc. Res. 27 (2005) 349–56.
[7] M.S. Konsta, S.P. Shah, Hydration and properties of novel blended cements based on cement kiln dust and blast furnace slag, Cem. Conc. Res.
33 (2003) 1269–76.
[8] K.L. Lin, The influence of municipal solid waste incinerator fly ash slag blendei in cement pastes, Cem. Conc. Res. 35 (2005) 979–86.
[9] W.D. Gluchowski, W. Zajtsew, W. Pachomow, Slag-alkaline cements and concrete; structures, properties, technological and economical
aspects of use, Silic. Ind. 48 (1983) 197–200.
[10] J. Žvironaitė, I. Pundienė, V. Antonovič, V. Balkevičius, Investigation of Peculiarities in the Hardening Process of Portland Cements with
Active Additives out of Waste, Materials Science (Medžiagotyra) 17(1) (2011) 73–9.
[11] S. Maschio, G. Tonello, L. Piani, E. Furlani, Fly and bottom ashes from biomass combustion as cement replacing component in mortars
production: Rheological behaviour of the pastes and materials compression strength. Chemosphere 85 (2011) 666–671.
[12] T.R. Naik, Tests of wood ash as a potential source for construction materials, Report No. CBU-1999-09. Milwaukee: UWM Center for By-
Products Utilization, Department of Civil Engineering and Mechanics, University of Wisconsin-Milwaukee, 1999, p. 61.
[13] B.A. Dockter, K.E. Eyelands, In: Development of management options for biomass combustion by products, International Ash Utilization
Symposium. Centre for Applied Energy Research, University of Kentucky, Paper no. 82, 2003.
[14] S. Wang, L. Baxter, Comprehensive study of biomass fly ash in concrete: strength, microscopy, kinetics and durability, Fuel Process Tech.
88 (2007) 1165–70.
[15] R. Rajamma, R.J. Ball, L.A. Tarelho, G.C. Allen, J.A. Labrincha, V.M. Ferreira, Characterisation and use of biomass fly ash in cement-
based materials, J Hazard Mater 172 (2009) 1049–60.
[16] R. Rajamma, J.A. Labrincha, V.M. Ferreira, Alkali activation of biomass fly ash–metakaolin blends, Fuel 98 (2012) 265–71.
[17] P.L. Owens, Fly ash and its usage in concrete, Concr. J. Concr. Soc. 13 (1979) 21–26.
[18] K.D. Stuart, D.A. Anderson, P.D. Cady, Compressive strength studies of Portland cement mortars containing fly ash and superplasticizers,
Cem. Concr. Res. 10 (1980) 823–832.
[19] R.A. Helmuth, Water-reducing properties of fly ash in cement pastes, mortars, and concretes, in Causes and Test Methods, ed. by. V. M.
Malhotra. Proceedings of 2nd CANMET?ACI International Conference on the Use of Fly Ash, Silica Fume, Slag, and Natural Pozzolans in
Concrete. Madrid, Spain. Apr. 21–25, 1986 (American Concrete Institute, Detroit, Special Publication SP-91), pp. 723–737.
[20] A.U. Elinwa, S.P. Ejeh, Effects of incorporation of sawdust incineration fly ash in cement pastes and mortars, J. Asian Archit. Build. Eng.
3(1) (2004) 1–7.
[21] A.U. Elinwa, Y.A. Mahmood, Ash from timber waste as cement replacement material, Cem. Concr. Compos. 24 (2002) 219–22.
[22] M. Abdullahi, Characteristics of wood ASH/OPC concrete, Leonardo Electron. J. Pract. Technol. (2006) 9–16.
[23] Y. Otsubo, S. Miyai, K. Umeya, Time-dependant flow of cement pastes, Cem. Conc. Res. 10 (1980) 631–638.
[24] P.F.G. Banfill, D.C. Saunders, On the viscosimetric examination of cement pastes, Cem. Concr. Res. 11 (1981) 363–370.
[25] P. Coussot, N. Roussel, Quantification de la thixotropie des materiaux cimentaires et de ses effets’ [in French], Revue Europeenne de Genie
Civil. 10 (2006) 45–63.