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Procedia Engineering 57 (2013) 53 – 62

11th International Conference on Modern Building Materials, Structures and Techniques,
MBMST 2013

Hydration of Cement Composites Containing Large Amount of Waste
Barbara Pacewskaa,*, Iwona Wilińskab

Warsaw University of Technology, Faculty of Civil Engineering, Mechanics and Petrochemistry, Lukasiewicza 17 St., 09-400 Plock, Poland

Reducing the consumption of cement with simultaneous utilizing waste materials is preferred for reasons of environmental protection.
Typical content of materials substituting cement in cement concrete composition does not exceed 35% of mass of binder. More and more
interest is aroused to the increase amount of cement supplements above 50%. The mechanism of hydration processes in such complex
systems is not fully understood. The aim of this work is to discuss possibilities of using binders with high amount of cement replacements,
with particular regard to physical and chemical processes occurring in such systems after addition of water. Based on literature reports
and our own research works possibilities of activation of binders containing high amount of cement replacement (e.g. fly ash) were
discussed. Further investigations concerning studies on mechanism of physical and chemical processes occurring in such mixtures are

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Keywords: upplementary cement materials; fly ash; pozzolana; activation; hydration.

1. Introduction
In connection with influence of cement industry on environment, different activities to minimalize emission of CO 2 as
well as consumption of energy and raw materials are introduced. Use of alternative fuels or optimization of heat transfer
during production of clinker may be mentioned as examples of such actions. Moreover using cements in which part of
clinker was replaced by other materials which are chemically active in hydrating cement system (so-called supplementary
cementing materials (SCM)) or by different fillers is widely accepted [1], [2]. Materials such as silica fume, fly ash, blast
furnace slag or natural pozzolan have been used for years as constituents of some types of cements (e.g. more widely used
CEM II according to PN-EN 197-1) or components introduced into concrete mixture on construction site. Proper application
of such reactive materials results in improvement of strength and durability of cement composite, especially in later periods
of hydration. For example, one of the advantages of cement concrete made with fly ash is low heat of hydration of the
binder, which limits temperature rise in the concrete, thereby reduces the risk of thermal stresses. Other known benefits of
proper use of fly ash are to increase the chemical resistance of concrete, and decrease susceptibility to alkali - aggregate
reaction [3].
Typical SCM content in cement composition does not exceed 35% of mass of binder. Meanwhile, in connection with
protection of the environment, more and more interest is aroused to the increasing amount of cement supplements (more
than 50%) and research on optimization of the composition of such mixtures. There is also a third group that can be

* Corresponding author.
E-mail address: bpacewska@pw.plock.pl

1877-7058 © 2013 The Authors. Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
Selection and peer-review under responsibility of the Vilnius Gediminas Technical University

H – H2O) [4]. For example. hydrates which arise. As a result. the reactivity of cement replacements is lower than for cement clinker. as well as influence of different factors on early and long-term properties of composites containing high amount of SCM seems to be still insufficient. which exhibit low initial activity and thus worsen early properties of final materials and require additional activating agents. AFt) as well as similar products with iron ions (some abbreviations used in cement chemistry: C – CaO. based on recent studies of literature and our own research works. However one cannot forget about other equally important processes. calcium hydroxide CH. Physical and chemical hydration processes occurring in such systems also will be different.g. hardened structure. There are large number of published in the world research works concerning composites made on the basis of blended binders (cement + SCM). evaporation.g. Kinetics of reaction of such materials in the hydrating cement environment depends on their chemical composition. They relate to mechanical properties of such materials. chemical. etc. Its specific action depends on the amount and type of cement and on the temperature (particularly in the case of calcium aluminate cement) [5]. [2]. the C-S-H phase formed with pozzolanic additive has a lower C/S ratio. phase and granulometric compositions of binder in the first case and temperature. As it can be expected. Activity of the aluminosilicate in hydrating cement paste is higher in the case of more fine-grained material compared to coarse-grained one. pH. The role of the conventional fly ashes during the hydration of cement is relatively well known. the cement paste with the addition contains a smaller amount of calcium hydroxide and a greater amount of phases of aluminate hydrates in comparison to the reference sample. contributing to the creation a more compact structure and obtain higher strength of cement-ash composite. S – SiO2. in the presence of spent aluminosilicate catalyst. with particular regard to physical and chemical processes occurring in such systems. the use of class C fly ash or slags in amounts of 70% is mentioned [8]. in the literature. [9]. In the early periods of hydration. adsorption. Chemical composition and reactivity of cement replacing material may also influence the amount of ettringite.g. also including a significant amount of cement replacements. resulting in increased capture of aluminum ions from a solution. The aim of this work is to discuss possibilities of using great amounts of SCM as components of cement composites. small or moderate amounts of fly ash accelerate hydration of cement. the presence of Ca(OH)2 is necessary for the reaction to form the products of the C-S-H and hydrated aluminates phases. in case when the amount of cement is insufficient. One of the most commonly used pozzolanic additives is fly ash. In fact. their durability.54 Barbara Pacewska and Iwona Wilińska / Procedia Engineering 57 (2013) 53 – 62 distinguished – non-cement binders made of 100% SCM hardening under the influence of high pH solution (geopolymers). in the second one). Non-reacted grains of fly ash act as micro-fillers. Moreover. The Ca(OH)2 may arise during cement hydration or. it can be concluded that SCM containing calcium compounds in their composition and exhibiting hydraulic or pozzolan-hydraulic properties (e. high calcium fly ash) can be introduced in higher amounts compared with those SCM that exhibit only pozzolanic activity. the amount of reactive phases (e. However knowledge about processes occurring during formation of dense. calcium hydroxide originating in the Portland cement hydration is bound in the pozzolanic reaction. Chemical reactions of hydration and their products play an important role in formation of microstructure of hardened material and its final properties. such as aggregation. it should be additionally introduced into the system. In most cases. It is well known that hydration of Portland cement results in formation of hydrated calcium silicates C-S-H. AFm phases such as monosulfate or monoaluminate as well as strätlingite [2]. amorphous silica). Both cement and introduced additives may interact on each other and modify their reactivity and products arising in the presence of water. which are incorporated into the structure of the C-S-H. as well as hydration processes. [6]. Products of this reaction fill the voids. More active batches act accelerating on cement hydration and on the rate and amount of heat generated during the early reaction of the binder with water. Spherical grains of fly ash act as agents for improving the rheological properties of fresh concrete mixtures. humidity. fineness. when one considers the fact that the new compositions of binders and composite materials are developed. temperature etc. It is especially evident. In general. blast furnace slag. It is assumed that in the presence of silica or aluminosilicate additives the hydration products are similar to those that are formed during the hydration of neat cement. The presence of fly ash also affects the kinetics of cement hydration. fly ash reacts with Ca(OH)2. Mixing cement with materials replacing it leads to complicate the systems in which cement hydration and pozzolanic or hydraulic reactions with SCM may occur at the same time. Hydration in the cement-additive system Processes occurring in cement-additive systems depend on different internal and external factors (e. 2. hydrated calcium aluminates and sulfoaluminates (AFm. [7]. chemically aggressive agents etc. In the later case. For example. composites containing large quantities of SCM will be characterized by different properties when compared to the features of concrete produced on the basis of a typical Portland cement. acting as nucleation centers for . The amount of material replacing cement in concrete depends largely on chemical and phase composition of SCM.

but after only 7 days the results are similar as for reference cement concrete and in later periods they are even higher. fly ash from fluidized coal combustion is characterized by high porosity and irregular shape of grains in contrast to spherical grains of conventional fly ash. For example. [9].g.Barbara Pacewska and Iwona Wilińska / Procedia Engineering 57 (2013) 53 – 62 precipitating the cement hydration products. also connected with improvement of properties of final cement composites. to obtain the best results. e. dicalcium silicate. e.g. However it should be emphasized that properties of fly ashes and thus their influence on cement hydration may be different depending on type of combusted fuel. Using this additive in higher amount (15%) results in some reduction of early strength. [18]. microsilica [9]. The rapid initiation of pozzolanic reaction between fly ash and Ca(OH)2 is conditioned by a high enough pH level allowing the dissolution of glass ash. However. [19]. Basing on the results presented in [9] one may state that introduction of a small amount of silica fume (as one additive) results in better development of strength of cement concrete compared to findings for reference sample. are the main problems. 3. The reason of this delay may be retardation of cement hydration as a result of interaction with fly ash and simultaneous significant reduction in the amount of cement. The diagnosis of physical and chemical processes responsible for the development characteristics of the composites is essential when considering the long-term properties of final materials. twofold interaction may be considered: activation of fly ash and acceleration of cement hydration. Composites containing high amount of SCM The proper use of SCM (including fly ash) results in many benefits.g. [17]. Replacement of significant part of cement by fly ash may result in reduction of alkalinity of water in pores of a composite. • introduction of additional components of the activation action. [18]. technology of desulfurization of gases etc. This decrease of alkalinity progresses during the hydration time [22]. and gypsum results in reduction of time of set of the mixture in which 50% of cement was replacement by fly ash. Thus. [17]. At last. Some activating additives increase the pH of water in pores of the material.g. e. • rapid set cement [21]. In the latter case. but it is very important to explain the mechanism of their action (especially the role of ettringite and other products of hydration) [21]. • complete replacement of typical Portland cement by a rapid hardening cement [16]. Research works that are carried out in this direction concern physical and chemical processes occurring in the presence of activating agent as well as properties of final hardened materials. Adsorption of Ca2+ ions on fly ash grains as well as increasing of availability of water to cement hydration may be also considered as mechanisms of early action of fly ash [10]. were used in the majority of works concerning application of chemical activating agents in high volume SCM concretes. Their action is complex. high volume fly ash concrete) elongation of time of setting and hardening as well as the slow strength development. the degree of fineness of the added material is essential.g. • calcium carbonate [1]. especially when it is different type than Portland cement.g. Great interest is aroused the progress of nanotechnology and nanomodification of cement composites in order to obtain improved 55 . one can mention the use of small amounts of: • active pozzolan e. [20]. e. superplasticizer and chemical activator. In some cases mixing of different additives is favorable and with combination with appropriate proportions of the other ingredients enables even obtain high performance concrete. Different literature reports indicate that actions mentioned below may be the effective remedies in such situations: • significant reduction in the water/binder ratio combined with the use of highly efficient superplasticizers. [21]. [15]. Different mechanism seems to take place when fast setting cement was used. [15]. Combined use of low water/binder ratio. but the favorable results were evident only after a certain period of hydration. In case of introducing of silica fume into binary binder containing cement and slag or cement and fly ash an increase of early strength was not observed. [14]. [18]. Influence of additionally added silica fume on development of properties of concrete is interesting. For example in the work [21] it was shown that application of Ca(OH)2 or rapid set cement based on calcium sulfoaluminate. As shown by numerous studies. both studied activators were effective in improvement of setting. Ashes of different origin may exhibit very different properties. in case of application of large quantities of cement replacements (over 50%. [11]. • intense grinding of fly ash resulting in development of its specific surface area and increasing susceptibility to the reaction and the reaction rate (improvement of pozzolanic activity). [19]. which is respectively: pozzolanic reaction and to fill free voids as well as sealing of aggregate – paste zone. e. conditions and technology of combustion. [11]. One may consider chemical and physical action of silica fume. Moreover such ashes have also different chemical and mineralogical composition (inter alia greater amount of calcium compounds). • calcium hydroxide [21]. Activity of fluidised fly ash in the environment of hydrating cement is typically higher than the conventional fly ash [12-13].

it is AFm and AFt phases. Its approximate oxide composition was as follow: 50% SiO2. 4. 5% CaO. Moreover. In the following part of this paper examples of results obtained for investigations of early hydration of pastes containing different amounts of fly ash were presented. In real conditions at the construction site such long curing is a problem. As it is known.F)*CaCO3*11H2O) than typical sulfate AFm phase [20] was preferred. an acceleration of hydration reaction in its early periods was observed when calcium carbonate of nano-grain size was used. This effect of acceleration of cement hydration and time of setting as well as improvement of strength by addition of nano-CaCO3 is to some degree depended on the way of comminution of CaCO3 particles [18]. additional introduction of slag as an aggregate allows to obtain high-strength concrete. Combined use of fly ash and nano-SiO2 in proper proportions may result in beneficial combined impact of the two materials: fly ash improves flowability of the mixture whereas nano-SiO2. However.The research conducted in [24].56 Barbara Pacewska and Iwona Wilińska / Procedia Engineering 57 (2013) 53 – 62 materials or products exhibiting new properties.replacement of a part of aggregate or both a part of cement and a part of aggregate. One may evaluate different compositions of concretes containing various amounts of components and then chose the best variant regard to the mechanical properties and durability. there are also other possibilities for utilization of high amount of industrial waste materials in cement concrete . • further research of early hydration is necessary to improve development of early properties of composites containing high amounts of SCM. Different mechanisms of effect of very fine-grained CaCO3 are considered: a nucleation action of fine filler and a providing an additional source of Ca 2+ ions [19]. Above. whereas nano-SiO 2 is characterized by developed surface area therefore its effect on the workability is opposite. 2013]. whereas fly ash concrete needs more rigorous curing compared with typical Portland cement concrete. Whereas. the influence of CaCO3 on fly ash-cement paste depends on inter alia an amount of CaCO3. In the work [23] results of investigations of highcalcium fly ash or slag used as alternative binders and another slag as alternative aggregate were described. For example. confirm significant reduction of mechanical properties of concrete when 50% of cement was substituted by class C fly ash. Moreover significant beneficial effect of the silica dust in ternary systems was not observed. [19]. 1% SO3 (mass%). It may be the result of binding of great amount of Ca(OH)2 in the early periods and thereby reduction of pozzolanic reaction with fly ash in the subsequent days. however in most cases 28-days curing in laboratory conditions was applied in these studies. an optimization of composition of concrete mixture is necessary to obtain the best parameters. its chemical action in the hydrating cement system has long been known. Such considerations are presented in [25]. The paper [23] may be a confirmation of such research. Calcium carbonate is often regarded as chemically inert filler. despite the beneficial effects of nano-SiO2 in the early stages of hydration. with concrete curing for 7 days. its granulometric composition as well as content of aluminate compounds in fly ash. that properties of cement composites depend on many factors. Formation of monocarbonate type of AFm (C3(A. exhibiting high reactivity. wherein both influence of the carbonate on cement hydration as well as on fly ash reactivity should be considered. application of cement substitutes was described. Calorimetry and thermal analysis were used as a good complementary research methods for preliminary assessment of the hydration progress. Chemical action of CaCO3 consists on interaction between hydrated sulfoaluminates. spherical grains of conventional fly ash improve workability of fresh concrete mixture. The use of slag only as the aggregate results in improved strength starting from the 7th day of hydration. Materials and methods Conventional fly ash coming from combustion of hard coal was used for investigation. 7% Fe2O3. However. the knowledge concerning the mechanisms of physical and chemical processes occurring in such systems seems to be still insufficient. In conclusion of brief review of the literature made above it can be stated that: • despite the large number of works devoted to the influence of cement substitutes on the development of properties of cement composites. raises the early mechanical properties of the composite [Kawashima et al.. while in case of more coarse fraction of CaCO3 (of mean diameter > 5μm) this effect was not registered [1]. • knowledge of the chemical and physical processes occurring in such complex systems is necessary to evaluate the longterm properties of the materials. Cement pastes with the addition . in the later periods it may cause some reduction of concrete strength. As noted by Kayali and co-authors [24] some literature reports indicate that high-performance high-strength concrete may be obtained by the use of high volume fly ash. . 20% Al2O3. It was also confirmed that action of nano-microsilica is more effective compared with typical silica fume [17]. It was affirmed that when using fly ash as 50% replacement of cement results in decreasing of 28-days strength. it should be pointed that. that arise during cement hydration. Taking into account. Particularly worth emphasizing is that nanoparticles can accelerate cement hydration processes and improve early-age mechanical characteristics [18].

In connection with this in the presence of CEM I 42. Cement CEM I 42. Two types of commercially available Portland cements were used: CEM I 32. 1-4. After appointed time the samples were ground and hydration was stopped by the use of acetone. KOH. hydration process may be observed continuously after adding water to cement. Na2SO4 or Ca(OH)2 were introduced in amount of 2% of binder mass. slow developing of its pozzolanic activity and low amount of cement. Calorimetry Calorimetry is a very good method for investigation of early cement hydration. heating rate 10oC/min. Cement pastes for calorimetric investigations were hydrated in sample vessel in calorimeter. nitrogen atmosphere. Using this method. higher compressive strength. Registered curves show total heat released during the time of experiment and rate of this heat evolution. during reaching the maximum . It can be seen.5R exhibits faster onset of setting. Samples for thermal analysis studies were put in polyethylene forms and stored in high humidity conditions and at 25°C. In a very general way the observed effects can be described as follows: 1) rapid release of small amounts of heat just after addition of water to binder (wetting of grains.5 for all investigated samples. 2) induction period (a slowdown of hydration processes explained inter alia by the formation of layers of products that coat the grains of cement. TA Instruments. 5. the start of hydration).5R and faster setting CEM I 42.5R.Barbara Pacewska and Iwona Wilińska / Procedia Engineering 57 (2013) 53 – 62 of the fly ash in amount of 40 and 80% of dry binder mass were performed. elongation of induction period and decrease of intensity of the next heat release effect compared with the reference sample (100% of cement) were observed. that the calorimetric curves exhibit typical shapes as for cement pastes containing high amounts of low active SCM. These chemicals were introduced as dissolved in water. Dry components of binders were hand-mixed and then proper amount of water was added. Basing on the shape of the calorimetric curve. Obtained results were presented in Figs. Water to binder ratio was 0. The results were calculated using computer software [26]. 57 . characteristic periods connected with physical and chemical processes occurring in the system may be distinguished [4]. Mentioned types of cement were also used in mixture 50:50 wt. with the relatively small difference in price compared to the cement CEM I 32.the end of setting may be observed). mass of sample: 9-13 mg. 5) period of slow growth of hydration products and thickening of structure with gradual disappearance of the cement components. NaOH. relatively high heat of hydration and high rate of rise of the early strength.5R better results were expected. dissolution. These cements were selected basing on differences of their properties. at the end of this period beginning of setting is observed). Total heat released after 48h of hydration was also decreased. These changes are especially visible when 80% of fly ash was used. This is an effect of delaying action of fly ash. Differential calorimeter constructed at the Institute of Physical Chemistry of Polish Academy of Science was used. Thermostat temperature was 25 °C. 3) renewed increase in heat release rate (fast crystallization of products. In case of cement pastes alkaline activated. • thermal analysis – TG and DTG curves were registered by the use of SDT 2960 Thermoanalyser. Research methods mentioned bellow were used: • calorimetry – the amount of heat released and rate of its evolution after adding water to binder were measured. 4) period of gradual decline of heat release rate (formation of the hardened structure). For samples containing fly ash. availability and price.5R.1. Results and discussion 5.

CEM mix Fig.5 6 40% fly ash.5R) exhibits slightly shorter induction period as compared with CEM I 32.CEM mix Fig. the induction period is similar for both samples (with two types of cements) but intensity of the effect connected with crystallization of formed products is higher for samples containing CEM I 42. In the case of using mixture of both cements (50:50) intermediate results were obtained.5 5 40% fly ash.5 7 9 80% fly ash. 1. However. effect of hydrates precipitation was more intensive and total heat released was also greater as compared with results for the same sample with CEM I 32. while intensity of heat release in the next period is higher but lower than for CEM I 42. Curves of heat release rate for cement pastes made of 0.5 8 80% fly ash.5 6 40% fly ash. CEM mix 7 80% fly ash. CEM I 42.5 R 3 100% CEM mix 4 40% fly ash. 40 and 80% of fly ash and with different cements As it was expected. the acceleration of early hydration periods compared with CEM I 32. CEM I 42. In case of 40% content of fly ash.5R.5 R 2 100% CEM I 42.5R.5 5 40% fly ash.Barbara Pacewska and Iwona Wilińska / Procedia Engineering 57 (2013) 53 – 62 dQ/dt (J/g/h) 16 2 12 6 3 1 5 8 4 4 8 9 7 0 0 10 20 30 time (h) 40 1 100% CEM I 32.5 8 80% fly ash. CEM I 32.5R. the induction period was significantly shorter. but after 48h the amount of heat released for sample with this mixture as well as with CEM I 32. For sample with 80% of fly ash and CEM I 42. faster set cement (CEM I 42.5R. In case of mixture of cements an intermediate effect was observed wherein induction period was almost the same as for the cement 32. Heat released for cement pastes made of 0. 40 and 80% of fly ash and with different cements . 2. CEM I 42. CEM I 32. CEM I 32.5 R 3 100% CEM mix 4 40% fly ash. CEM mix 80% fly ash. CEM I 42. CEM I 32. These dependencies are also reflected in the course of hydration of pastes containing fly ash. it should be noted that in the case of mix cements. 300 Heat released (J/g) 58 200 2 3 1 100 5 4 6 9 0 0 10 20 30 8 7 40 time (h) 1 100% CEM I 32.5R.5R.5 R 2 100% CEM I 42.5 9 80% fly ash.5R was observed.5R only was practically the same.

CEM I 32. For cement pastes containing these admixtures some reduction of induction period and increase of heat released as compared to sample with 80% of fly ash and without additional chemical reagents were observed. it is the sample prepared with 80% of fly ash and CEM I 32. Heat released for alkaline activated cement pastes (80% of fly ash. its amount and to investigate a mechanism of this action and types of arising hydration products.5 2 80% fly ash. 4. 3. and it should be also consider.5R. However this effect of acceleration does not reach intensity of hydration registered for fly ash and CEM I 42. CEM I 42. was performed (Figs. 3-4).5 3 80% fly ash + 2% NaOH 4 80% fly ash + 2% Na2SO4 5 80% fly ash + 2%KOH 6 80% fly ash + 2% Ca(OH)2 Heat released (J/g) Fig. CEM I 32. CEM I 32.5R) and non-activated sample made of fly ash and CEM I 42. This part of research requires further investigation to select the best activator. CEM I 32. Na2SO4 and NaOH can accelerate early hydration of cement pastes containing moderate amount of fly ash addition.Barbara Pacewska and Iwona Wilińska / Procedia Engineering 57 (2013) 53 – 62 It was confirmed in earlier studies that application of small amounts of chemical reagents such as CaCl2.5R.5 2 80% fly ash.5R) and non-activated sample made of fly ash and CEM I 42. However introduction of additional amounts of alkaline reagents may increase the risk of alkaline corrosion (ASR) in presence of some aggregates. CEM I 42. 6 dQ/dt (J/g/h) 5 4 3 2 2 1 3 4 1 0 0 10 5 6 20 30 40 time (h) 1 80% fly ash. Between activators that were used only NaOH and in low degree Na2SO4 show activating action. but the mechanism of activators action is different for each of them [27].5 3 80% fly ash + 2% NaOH 4 80% fly ash + 2% Na2SO4 5 80% fly ash + 2%KOH 6 80% fly ash + 2% Ca(OH)2 Fig.5R 2 60 3 40 20 5 0 0 10 1 4 20 6 30 40 time (h) 1 80% fly ash. In this work an attempt of alkaline activation of cement paste exhibiting the lowest rate of hydration. Comparison of calorimetric curves for alkaline activated cement pastes (80% of fly ash.5R 59 .

5R. It was affirmed. At later days the amount of bound water for samples with fly ash increases. However on 28th day of hydration the results obtained for both types of cements are similar. resulting from the reduced amount of cement (lower amount of water was bound in formed products and in Ca(OH) 2). In later days.5R hydration processes undergo more rapid in comparison with 32. Thus. In case of using of different types of Portland cements observed differences relate mainly to the quantities of each groups of products. The effect of some delay of hydration is also observed. that in case of CEM I 42.60 Barbara Pacewska and Iwona Wilińska / Procedia Engineering 57 (2013) 53 – 62 The results of currently performed researches suggest that it may be advantageous to replace part of fly ash by an active pozzolan. There are three major weight losses: • up to about 420 °C – dehydration of hydrated forms type of silicates C-S-H. and the amount of ettringite starts to decrease. and then monosulphate begins to appear. • at temp. Progress of hydration of cement CEM I 32.5 R and mixture of cements strength of cement paste containing fly ash may be initially higher than in the case of cement CEM I 32. and then it is separated again at a slightly higher temperature. Moreover in presence of 10% of the aluminosilicate the heat release during first 4h is more intensive and it is similar to the reference sample. In the case of cement CEM I 32. This effect is visible in results registered after 24h of hydration. • above 470 °C – decomposition of carbonates. . which is shown in the DTG curve recorded after 28 days of hydration. These changes can be explained as follows: probably till 24h of hydration residues of gypsum continue the reaction in the direction of ettringite. 5 and 6. In the initial hydration period. However. it was confirmed. greater amounts of water combined in hydrates as well as Ca(OH)2 were observed for cement pastes made of 40% of fly ash and CEM I 42.5 R and mixtures of cements the effect at about 120oC is not detected after 24h of hydration. In case of large amounts of fly ash.5R the effect on DTG curve at about 120oC was observed. In the case of cement CEM I 42. but in the later days it “catches up” hydration of the cement 42. For example. 6. this faster hydration appears by greater amount of water combined in hydrates (the first mass loss to about 420oC) and greater content of Ca(OH)2 (the amount of Ca(OH)2 in the sample is proportional to the weight loss related to the decomposition at about 420-470 °C).5 R. Amount of Ca(OH)2 increases till 7 days of hydration.5 R the effect suggesting presence of unreacted gypsum is still visible. which can be a waste aluminosilicate catalyst. reduction in observed mass losses.5R. and after 28 days it is almost not observable. It disappears in the subsequent days. about 420–470 °C – decomposition of Ca(OH)2. Promoting role of faster cement is less pronounced on 1st day but larger differences are visible after 7 days. Thus.5 R is more moderate. in the presence of 10% of this aluminosilicate (at 70% of fly ash) the induction period undergo some reduction and next effect of heat release (crystallization of the products) is more pronounced compared with results for binder containing 80% of fly ash. Introduction of 40 wt% of fly ash as a cement replacement results. it may confirmed that Portland cement CEM I 42. whereas amount of Ca(OH)2 increases till 7th day of hydration and then decreases. but at a later days these differences will decrease. This effect is not observed for cement pastes performed with CEM I 42.5R in comparison with the results for analogous samples of cement CEM I 32. In general. The obtained results allow to suppose that in the case of cement CEM I 42. that is visible at the first days of hydration (till 7th day). it is after one day. For the mixture of cements intermediate results were obtained.5R is characterized by faster early hydration in comparison with CEM I 32. Starting from 7th day of hydration thermal analysis does not show qualitative differences in the composition of the samples.5R. It confirms pozzolanic activity of fly ash. Thermal analysis The obtained results (examples of TG and DTG curves) as well as mass losses at individual ranges of temperature were presented in Figs. Comparison of the amounts of water combined in hydrates and Ca(OH)2 for cement pastes containing 40% of fly ash and for adequate reference samples suggests that in initial periods fly ash acts mainly as filler and its eventual acceleration of cement hydration is inconsiderable. which results faster setting and achieving higher early strength. as expected. these differences are less pronounced. then begins to decrease.5R and mixture of both of cements. after one day of hydration of the sample made of CEM I 32. which is 80% of the mass of dry binder. The total amount of heat evolved during 48h of hydration is also greater as compared with the case when fly ash is used only.5 R. reducing the amount of formed products is even bigger. that shapes of TG and DTG curves for all investigated samples are typical as for Portland cement pastes. hydrated aluminates and sulfoaluminates.

Conclusions 1. It results in elongation of setting and reduction of early strength especially in cases where the cement is replaced in large quantities.5R 42. There is a need for research related to the possibilities of exchange of the cement in concrete or search for new alternative binders. chemical and phase composition. especially when industrial waste is used as cement replacement.5R 42. hardening and mechanical properties in the initial periods.5R mix 32. 3.g. It is especially visible when high amounts of fly ash is used. the effect of unique properties of examined mixtures.5R 42. Mass losses for cement pastes at particular ranges of temperatures ( a – up to 420oC. 5.5R mix 32.61 Barbara Pacewska and Iwona Wilińska / Procedia Engineering 57 (2013) 53 – 62 Fig. Understanding the physical and chemical processes taking place in the new binders is necessary to evaluation of their long-term properties. 2. The mechanism of hydration processes in such complex systems is not fully understood.5R mix 32. . inter alia. which is.5R mix 32. 4. 5. It was confirmed that introduction of fly ash results in retardation of hydration especially in its early periods. Examples of TG and DTG curves for cement pastes (1st day of hydration) b) 100 % CEM 18 16 14 12 10 8 6 4 2 0 40 % fly ash 80 % fly ash Mass loss / % Mass loss / % a) 20 6 5 100 % CEM 40 % fly ash 80 % fly ash 4 3 2 1 0 CEM CEM CEM CEM CEM CEM CEM CEM CEM 32. Cement replacement materials often exhibit lower activity than the cement alone.5R mix Type of cement 1d 7d 28 d Fig. Reducing the consumption of cement with simultaneous utilizing waste materials is preferred for reasons of environmental protection.5R 42.5R mix Type of cement 1d 7d 28 d CEM CEM CEM CEM CEM CEM CEM CEM CEM 32. It is advantageous to develop methods of activation of high volume fly ash binder. Such research works should be undertaken and continued. such as e.5R 42. efficiently improving setting. 6. b – 420 – 470 °C) 7.5R 42.

Materials and Design 46: 301–309. 377-385. 2010. Kraków. J. Grondin.. pp.conbuildmat. Wilińska. Sharfuddin Ahmed. S. Computer software for processing of data obtained from calorimeter [27] Pacewska.1016/S0008-8846(03)00150-9 [16] McCarthy. Volz. 292-299....-H.09. doi:10.1016/j.2012..08. J. Li. pp.fuel.. K. K. S..1016/j. Mix design of concrete with high content of mineral additions: Optimisation to improve early age strength. 2009.016 [24] Kayali.2010. 2012. M. U.11. Wilińska. P. pp.045 [10] Zeng. doi:10. 1423-1432. 2008. 71-76. Calorimetry and thermal analysis are good complementary methods to the preliminary assessment of the progress of hydration modified cement pastes.D. H. M. Cement and Concrete Research 34. Bukowska.01. E. K. Supplementary cementitious materials. doi:10. Sun.. Journal of Thermal Analysis and Calorimetry 93(3). W..doi:10. 265-270. 279-291. Assessment of high volume replacement fly ash concrete – Concept of performance index. Naukowe PWN. Schwesig. Cement and Concrete Composites 33. A. M. H. Journal of Thermal Analysis and Calorimetry 86(1). Nocuń-Wczelik W. K.1007/s10973-008-9179-8 [14] Jackiewicz-Rek. J. I. doi: 10.. R.. [6] Pacewska. Mechanical and durability properties of high performance concretes containing supplementary cementitious materials. T.. 11-17. Construction and Building Materials 29. Sata.. 2006. G.. pp. Cement and Concrete Research 42. doi: 10. Investinagtions of the influence of different fly ashes on cement hydration.. V. Journal of Thermal Analysis and Calorimetry 97(1). 2005.. Justnes.2010.1016/j. Hydration mechanisms of ternary Portland cements containing limestone powder and fly ash. A. Hydration of high-volume fly ash cement pastes. Use of nano-silica to reduce setting time and increase early strength of concretes with high volumes of fly ash or slag. 179–186... 2010. Sellevold. pp. It may be advantageous to usage more rapid set cement. Dangla. Use of calorimetry and infrared absorption methods. T. S.. Chemia cementu i betonu. 2010.1016/j.. W.2010. 399-425 (in Polish) [4] Kurdowski. Construction and Building Materials 39. Q. Cement & Concrete Composites 34.. P.2010. 549-555.1007/s10673-005-7136-7 [13] Pacewska. Konferencja Dni Betonu. A. resulting in acceleration of occurring reaction compared with cement CEM I 32. I.cemconcomp. pp.. 1412–1417.. C.01. B.008 [22] Zhang. 2013.1016/j. Seufert. Sato.09.1016/j.... 2012. C. 2012. pp. P. Wyd. Wilińska. J. 2004. Loukili.2012. Winnefeld. References [1] De Weerdt.07. 1389-1400. Journal of Thermal Analysis and Calorimetry 77. Myers.. doi: 10. Hou.06. Ferraris.2004. S.. Construction and Building Materials 27. 2013. 573-580. 2011.. W. Weiss...62 Barbara Pacewska and Iwona Wilińska / Procedia Engineering 57 (2013) 53 – 62 6.. G.009 [12] Pacewska. doi:10. 2011.1007/s10973-008-9143-7 .. 2010.009 [25] Khokhar. I.004 [20] De Weerdt.5R. Islam...12. Cement and Concrete Research 41. Lothenbach. 8.. pp. Yan. doi:10. P.001 [3] Czarnecki. Kiattikomol. Dittrich. H. Journal of Thermal Analysis and Calorimetry 94(2). Ortega. [7] Pacewska.. M.. trwały beton. P. pp. J.1016/j. pp... Cement and Concrete Research 32. Stowarzyszenie Producentów Cementu. D. 2008.cemconcomp. Construction and Building Materials 24.. Wyd. pp.conbuildmat. B. doi: 10.029 [17] Zhang. [23] Papayianni.conbuildmat. M. G. Use of ground coarse fly ash as a replacement of condensed silica fume in producing high-strength concrete. Blonkowski.. L... pp. Kjellsen.cemconcomp. J.. doi:10. Materiały Budowlane (10). 2010.. Effect of total cementitious content on shear strength of high-volume fly ash concrete beams. B.1016/j. T. I. B. Wilińska..2011. Justnes. Bukowska. Wilińska. Shah. Khan.cemconcomp. Cement & Concrete Composites 32. I.. 1823-1830. 769-776. Hooton. P. An attempt to improve the pozzolanic activity of waste aluminosilicate catalyst. Basheer.2009. D. Modification of cement-based materials with nanoparticles.. pp. 2010. Construction and Building Materials 24.. Bukowska..1016/j. Ben Haha. K.1016/j. Nanukuttan. A.. W.014 [21] Bentz. pp. Some acceleration can also be achieved when the fast set cement is used as a component of mixture of cements.. pp. Effect of waste aluminosilicate material on cement hydration and properties of cement mortars.. V. 2012. doi: 10. Fuel 84. pp. pp. K. D.conbuildmat. O. doi:10... P. 2004. Le Saout.. 2000.cemconres. B. F.2011. 469-476. 2002. B.1016/j..1016/j. pp. Development of high volume fly ash cements for use in concrete construction. doi:10. F.031 [9] Elahi. Wilińska.. B.. Y.1007/s10973-008-9668-9 [8] Arezoumandi. pp. Calorimetric investigations of the influence of waste aluminosilicate on the hydration of different cements...2012. C.conbuildmat. doi:10. 217-229. Kraków 2010 (in Polish) [5] Pacewska.. 560-569. G. M. 2013. J. 61-66... B. Corr.matdes. M. O. F. Determination of cement hydration and pozzolanic reaction extents for fly-ash cement pastes.. doi: 10. Neubauer. M. I.2010.01. Synergy between fly ash and limestone powder in ternary cements. W.. F.. Blonkowski. Lothenbach. Cement & Concrete Composites 36: 8–15. Fine limestone additions to regulate setting in high volume fly ash mixtures. pp. M. de la Varga. R. 133-142. 7. Polski Cement. Roziere. H.. Justnes. I.006 [2] Lothenbach. doi: 10..06. Production of high-strength concrete using high volume of industrial by-products. Rheology and setting of high volume fly ash mixtures. I...1016/j. Blonkowski.2011. Betony wysokopopiołowe.1016/j. D.. Anastasiou. Cement & Concrete Composites 32..013 [18] Kawashima.cemconres.05..08. B.. M.10. Blonkowski. O..2012. Fen-chong. G. P. A.007 [11] Deschner. J. Small activating effect was also observed in case of usage of Na2SO4 admixture. Calorimetry measurements show that using admixture of NaOH some shortening of induction period and intensification of hydration may be observed in the case of high volume fly ash binders. Leekeeratikul. doi: 10. S. Dhir.2010. 2012.. Hydration of Portland cement with high replacement by siliceous fly ash. Zrównoważony. K. K. Studies on the pozzolanic and hydraulic properties of fly ashes in model systems.. Q.. Cement & Concrete Composites 22. 2011.11.1016/j.. Kjellsen. Goetz-Neunhoeffer. 18-20 (in Polish) [15] Jaturapitakkul.cemconres. E. 30-38.. Z. Scrivener. S. M. 445-452... Nocuń-Wczelik. Cement and Concrete Research 41. E. F. doi: 10.012 [19] Bentz. doi: 10. I. Turcry. 2012. Investigations of cement early hydration in the presence of chemically activated fly ash... pp. pp.006 [26] Poznański. J. pp.cemconcomp.