Advances in Cement Research Volume 24 Issue 5 Inuence of metal chloride salts on calcium aluminate cement hydration Ukrainczyk, Vrbos

bos and Sipusic

Advances in Cement Research, 2012, 24(5), 249262 http://dx.doi.org/10.1680/adcr.11.00012 Paper 1100012 Received 08/03/2011; revised 20/07/2011; accepted 17/08/2011 Thomas Telford Ltd & 2012

Inuence of metal chloride salts on calcium aluminate cement hydration

Neven Ukrainczyk
Post-doctoral Researcher, Faculty of Chemical Engineering and Technology, University of Zagreb, Zagreb, Croatia

Juraj Sipusic
Associate Professor, Faculty of Chemical Engineering and Technology, University of Zagreb, Zagreb, Croatia

Nevenka Vrbos
Assistant Professor, Faculty of Chemical Engineering and Technology, University of Zagreb, Zagreb, Croatia

In this paper the inuence of alkali, alkaline earth and transition metals in the form of chlorides salts on the hydration of commercial iron-rich calcium aluminate cement (CAC) is investigated. The effect on setting time and mechanical properties is studied. The results of the setting time obtained from the measured temperature evolution of cement pastes are compared to standard Vicat needle measurements. Addition of alkali metal salts both accelerates the setting time of CAC and deteriorates long-term strengths in the order of decreasing ionic radius of the metals. The effect of alkaline earth metal salts on setting behaviour depends on the amount of addition: low concentrations retard, but high concentrations accelerate setting behaviour. Calcium is found to have the strongest acceleration effect with the lowest deterioration in strength. An interesting regularity is observed when plotting the results of both retarded setting times and strengths against atomic number of added transition metal cation.

Notation
A a, b C CAC F H K m M PC pK R R rn S T t ti tf tmax t0 w w/c Z aluminium oxide (Al2 O3 ) tting parameters calcium oxide (CaO) calcium aluminate cement iron oxide (Fe2 O3 ) water (H2 O) equilibrium constant cement mass (g) molar mass (g/mol) Portland cement log (K) ionic radius correlation coefcient nucleation rate (s1 ) silica (SiO2 ) temperature (8C) time (h) time of initial setting obtained by Vicat measurement time of nal setting obtained by Vicat measurement time of peak maxima in calorimetric measurement time of initial setting obtained by calorimetric measurement mass fraction of added salt relative to weight of cement (%) water-to-cement mass ratio atomic number

molar concentration of added salt per kg of cement (mmol/kg)

Introduction
The duration of the suitable workability of cement-based materials during placement is dened by setting time. The use of additives to modify the properties of cement-based materials for each specic application is a subject of great practical and nancial interest. From practice, it is known that even small amounts of different organic and inorganic compounds have a pronounced inuence on the setting behaviour and mechanical properties of cement-based materials. Calcium aluminate cement (CAC) as a special cement is particularly interesting because of its versatility in high-performance applications (Bensted, 2002; George, 1983; Mangabhai, 1990; Mangabhai and Glasser, 2001; Scrivener et al., 1999), such as those requiring: high early strength, resistance to chemical attack, resistance to abrasion, refractory properties and/or low ambient temperature placement. In comparison to commonly used Portland cement (PC), CACs show relatively slow setting but rapid hardening characteristics. These excellent properties make CAC products useful for rapid repairs of roads, hydraulic dams, industrial oors, pipe linings and other such purposes (Scrivener et al., 1999). Hydraulic hardening of CAC is primarily due to the hydration of CA (cement notation: C calcium oxide (CaO), A aluminium oxide (Al2 O3 ), F iron oxide (Fe2 O3 ), S silica (SiO2 ), 249

Advances in Cement Research Volume 24 Issue 5

Inuence of metal chloride salts on calcium aluminate cement hydration Ukrainczyk, Vrbos and Sipusic

H water (H2 O)), but other compounds may also participate in the hardening process, especially in long-term strength development (Ukrainczyk, 2010; Ukrainczyk and Matusinovic, 2010). The hydration of CAC is highly temperature dependent, yielding morphologically different hydration products at different temperatures of hydration. At ambient temperature metastabile hydrates, CAH10 and C2 AH8 (Ukrainczyk et al., 2007) transform to the more stable C3 AH6 and AH3 with consequent material porosity, permeability increase and loss of strength. The transformation is accelerated by temperature and moisture availability for the dissolution and re-precipitation processes to take place (Mangabhai and Glasser, 2001). Along with rapid setting, some metal salts result in the rapid strength development of CACs at very early ages, so they are advantageously used for rapid repair works of highways and airport runways (Justnes, 2008). The inuence of metal salts on cement hydration, particularly setting time and compressive strengths, is also of interest in stabilisation of hazardous waste containing potentially soluble heavy metals (Jantzen et al., 2010). Upon water addition to cement a sharp increase of the pH of the water solution occurs, less for CAC than for PC hydration, which causes precipitation of highly insoluble metal oxidehydroxide, thus opening an attractive route for heavy metal waste stabilisation. Lastly, the role of foreign ion additions in the nucleation and growth process of hydration products provides a fundamental insight into this intricate and enigmatic process. The admixtures can interfere with hydration of cement in a variety of ways. A number of different mechanisms have been suggested (e.g. Currell et al., 1987; Murat and Sadok, 1991; Rodger and Double, 1984) to explain the action of set regulators on cement hydration, mainly with respect to the dissolution of anhydrous cement, and the nucleation and precipitation processes for the main hydration products. The inuence of the particular additive on setting behaviour of CAC is generally not so well understood and contradictorily statements can be found in the literature, as detailed below. Part of the controversy could arise primarily from differences in the cement composition, the measurement technique employed and the conditions of hydration. Rodger and Double (1984) studied the inuence of alkali, alkaline earth and transition metal chlorides additions (25 mmol of salts per kg of cement) on setting of iron-rich CAC pastes prepared with a water-to-cement ratio (w/c) of 0.5 by measuring the maximum temperature rise in a semi-adiabatic calorimeter (T 22 28C, T . 1008C). A similar chemical composition of CAC is used in the present work (with 10% F (iron oxide)) but from a different producer, namely Lafarge Ciment Fondu. The summarised effect on setting time is in the following series: Li ,, Mg2 , Ba2 , none , K , Na , Sr2 , Ca2 : Furthermore, Rodger and Double reported that all transition metals chloride salts have a retarding effect on the set of CAC. Using a semi-adiabatic calorimeter (T 18 28C, T , 208C) Currell et al. (1987) investigated the setting of iron-rich CAC 250

(manufactured by Lafarge, with a relatively low iron oxide content of 6% compared with the CAC used in the present study) pastes with a w/c 0.27 in the presence of many additives with different concentrations. The effects on the setting time may be summarised as follows: Li ,, Na , none , K , Ca , Mg2 , Sr2 : Grifths et al. (1991) studied the setting of iron-rich CAC (Lafarge, similar chemical composition as in the present work except for somewhat lower iron oxide content at 10%) pastes (w/c 0.4) at different temperatures in the presence of 15 mmol/kg metal chlorides and sulfates, as well as sea water. Using the time corresponding to the maximal rate of heat generation to compare the setting behaviour in the presence of chlorides, they reported the following order at the various temperatures: Mg2 , K , Na , Ba2 , none , Ca2 at 158C; Mg2 , K , Na , none , Ca2 , Ba2 at 208C and 308C. The literature regarding the inuence of alkali and alkaline earth metal chlorides on the hydration of iron-rich CAC is confusing. The above-stated conicting results can be summarised as follows. For alkali chlorides sodium (Na) and potassium (K) are reported to act as both retarders and accelerators. For alkaline earth metal chlorides magnesium (Mg) acts as an accelerator, according to Rodger and Double (1984), and as a retarder, according to Currell et al. (1987). Only Rodger and Double (1984) investigated the effect of both strontium (Sr) and barium (Ba), which were reported to act differently, that is as retarder and accelerator, respectively. Although the inuence of admixtures on setting behaviour of iron-rich and refractory Secar 71 CACs, as two different classes of CACs, has been compared in the literature, care should be taken because they differ substantially in their properties (principally chemical and mineralogical composition). Murat and Sadok (1991) considered the role of foreign cations in the hydration kinetics of refractory CAC (Secar 71, produced by Lafarge, that has an aluminium oxide (Al2 O3 ) content of about 70%). They concluded that all chlorides metal salts (mono-, bi-, tri- and tetravalent) have an accelerating effect on the set of Secar 71. This result differs from most other studies summarised above. Nilforoushan and Sharp (1995) investigated the setting of Secar 71 with a range of concentrations (12.5250 mmol/kg) of alkaline earth metal chloride salts at different temperatures. At 128C all of the alkaline earth metal chlorides investigated exhibited retardation of setting, which increased with increasing concentration of the admixture. At 208C, at low concentrations, they were shown to accelerate the setting, but they acted as retarders at higher concentrations. At 288C and 368C, they retarded the setting, the more so with increasing concentration of the admixture. In the present paper, the authors have studied the inuence of alkali, alkaline earth and transition metal chlorides additions on setting behaviour as well as strength development of commercial iron-rich CAC.

Advances in Cement Research Volume 24 Issue 5

Inuence of metal chloride salts on calcium aluminate cement hydration Ukrainczyk, Vrbos and Sipusic

Experimental work
Materials This paper examines the hydration of three samples of commercial CAC ISTRA 40 taken from a regular production of Calucem, Pula, Croatia. The cement has the oxide mass fraction composition listed in Table 1. Physical properties of the cement are given in Table 2. The effect of alkali, alkaline earth and transition metal chlorides was studied on cement samples A, E and T, respectively. The main compounds are CA and ferrite phase (C4 AF C6 AF2 ), with mayenite, C12 A7 , gehlenite, C2 AS, and -C2 S as minor compounds. All specimens were prepared with a water-tocement mass ratio (w/c) that corresponds to a water requirement for the standard consistency (given in Table 2). The salts used as additives were commercial Analar grade reagents, dissolved in freshly deionised water before mixing with the cement. Alkali metal salts, NaCl, KCl, RbCl and CsCl, were mixed with a mass fraction (relative to weight of cement) of 0.05% and molar concentration of 3 mmol/kg of cement, and LiCl from 0.00025 to 0.50% (0.06118 mmol/kg). Alkaline earth metal salts: MgCl2 6H2 O, CaCl2 , SrCl2 6H2 O and i BaCl2 2H2 O, were mixed with mass ratios (relative to weight of cement) of 0.10, 0.50, 1.0, 2.0 and 5.0%. Transition metal salts, MnCl2 H2 O, CoCl2 6H2 O, CuCl2 2H2 O and ZnCl2 , were studied at 10 and 100 mmol/kg of cement. To prepare the samples of pastes the additives were weighed into deionised water according to a specied concentration and then mixed with cement. Mechanical properties Cement paste specimens (40 3 40 3 160 mm) were prepared according to ASTM C 109 (with a standard consistency). Bending and compression tests at different ages were done according to EN 1015-11. Three specimens were tested for each age. Sample A E T CaO 37.10 40.2 39.12 Al2 O3 38.47 39.0 37.78 Fe2 O3 14.39 11.7 13.17 FeO 2.90 4.3 2.46 SiO2 4.43 1.9 4.42

Setting time measurement The setting time was determined using the standard Vicat needle method carried out according to EN 196-3. The experiments used a standard consistency CAC paste, as given in Table 2. CAC temperature evolution measurement set-up The specimens were cast in high-density polyethylene containers with inner diameter 2R 31 mm, 50 mm high and 0.7 mm thick. The high-density polyethylene container was fully lled with the cement paste (with a standard consistency), continuously applying vibrations in order to minimise air entrapment. The thermocouple measuring end was placed exactly at the centre of the container (r 0 and z h/2 as shown in Figure 1). This was designed by xing a thin (1.3 mm), wooden support at the axis of the container. Specimens were carefully sealed with lids and polyvinyl chloride electrical insulation tape and placed vertically in the temperature-controlled water bath T 208C (0.038C). Before mixing, the cement and water components were left to reach thermal equilibrium (overnight) in a sealed container placed in a thermostat. Temperature evolution measurements were also performed simultaneously on the specimens tested for setting time, using a standard Vicat apparatus. After the Vicat mould (DIN standardised truncated conical form: 75 mm in diameter at the base, 65 mm at the top and 40 mm high, made up from non-absorbent plastic with a glass base plate) was lled with the cement paste, the thermocouple sensing end was placed at the weight centre, that is through the axis at half-thickness of the specimen. This was done by immersing a thin (1.3 mm) wooden support through the axis of the paste in the mould. Specimens were tested at laboratory conditions of T 20 28C. The K-type thermocouples used were 0.2 mm thick with TiO2 1.05 n.a. 1.80 MgO 0.90 n.a. 0.91 SO3 0.20 n.a. 0.30 Na2 O 0.14 0.13 0.18 K2 O 0.17 0.16 0.17 Sum 99.8 97.4 100.3

Table 1. Chemical composition of investigated CAC

Sample

.90 m: %

,40 m: %

Blaine, cm2 /g

Specic gravity: g/cm3 3.19 3.19 3.20

Setting time: min Initial 264 300 209 Final 279 322 236

Water-to-cement mass ratio of standard consistency 0.240 0.240 0.250

A E T

3.76 3.70 3.71

80.50 80.10 80.90

3407 3421 3563

Table 2. Physical properties of investigated CAC

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Inuence of metal chloride salts on calcium aluminate cement hydration Ukrainczyk, Vrbos and Sipusic

Motor Thermostat Cooling

Pt100 data logger PC TC data logger

Pt 100 Vicat needle r h T constant 2R

Figure 1. Schematic diagram of the CAC paste temperature evolution measurement set-up

grounded, twisted-shielded wiring. An eight-channel data logger with a 20 bit resolution was used to collect the temperature measurements. This stores the entire set of temperatures once every second. The experimental data are simultaneously transferred to a personal computer. The cold junction temperature held at room temperature was sensed by a precision thermistor in good thermal contact with the input connectors (on thermal block) of the measuring instrument. In order to have accurate cold junction compensation, any change of its temperature was kept as slow as possible.

w (LiCl): % 0 0.00025 0.00050 0.00075 0.0010 0.0025 0.0050 0.0075 0.010 0.025 0.050 0.10 0.50

: mmol/kg 0 0.06 0.12 0.18 0.24 0.59 1.18 1.77 2.36 5.90 11.8 23.6 118

ti : s 15840 13800 10560 9930 9545 4330 3030 1060 790 338 270 F I

tf : s 16720 15000 11330 10850 10267 5750 3700 1810 1433 413 293 F I

Results and discussion

Alkali metals Measurements of the Vicat initial and nal setting times, that is ti and tf respectively, were obtained as described in the Setting time measurement section. The effect of addition of lithium chloride (LiCl) in a range of concentrations from 0 to 118 mmol/kg on the setting of CAC is presented in Table 3. The data show that lithium chloride accelerates the setting time of CAC even for very low additions of only w 2.5 3 104 %, which corresponds to a molar concentration of 0.06 mmol/kg. As the addition of LiCl increases, both of the setting time parameters continuously decrease. With the mass fraction of 0.1% the setting time occurs during the mixing time, whereas with the fraction of 0.5% the setting of CAC occurs immediately after the addition of lithium chloride. The results on the investigated effect of various alkali metal chlorides on the setting time of CAC are presented in Table 4. It is obvious that lithium metal shows a drastic effect of acceleration in comparison to other alkali metals. The reason for this is discussed next. 252

Note: F denotes setting of the CAC with lithium chloride during the mixing; I denotes setting of the CAC immediately after addition of lithium chloride

Table 3. Comparison of setting time for different quantities of lithium chloride addition

The hydration process of CA, as the principal mineral in CAC, is generally believed to occur through initial dissolution, formation of a metastable gel and subsequent precipitation (Sorrentino et al., 1995; Taylor, 1998), principally CAH10 : After dissociation of CA, the metastable gel formed will acquire stability by condensation of mono-coordinated hydroxyl groups linked to aluminium to form ox-obridges between two aluminium centres, leading to the crystalline CAH10 : Solid-state nuclear magnetic resonance

Advances in Cement Research Volume 24 Issue 5

Inuence of metal chloride salts on calcium aluminate cement hydration Ukrainczyk, Vrbos and Sipusic

w 0.05% ti : s Lithium chloride Sodium chloride Potassium chloride Rubidium chloride Caesium chloride 270 8560 10 727 11 860 11 940 tf : s 293 8860 11 357 12 560 12 820 ti : s 712 10 960 12 027 11 965 11 940

3 mmol/kg tf : s 1371 11 293 12 927 12 660 12 820

Table 4. Comparison of setting times parameters for alkali metal chlorides additions (0.05% mass fraction and 3 mmol/kg)

Flexural strength: MPa

imaging data indicate that aluminium in CA is entirely fourcoordinated, but the hydration products of CA, CAH10 and C3 AH6 contain six-coordinated aluminium (Taylor, 1998), while C2 AH8 also contains four-coordinated aluminium located in the interlayer of this double-layer hydroxide phase (Ukrainczyk et al., 2007). Cong and Kirkpatrick (1993) have shown that the hydration of CAC proceeds by way of conversion of four to six-fold coordinated aluminium and the occurrence of intermediate phases, which still need further clarication. The ox-obridge condensed structure will be affected by alkali metal cations forming coordination linkage with the hydroxyl groups (Currell et al., 1987). Of the alkali ions studied, Li behaves differently from the other alkali cations because of its ability to form tetrahedral symmetry with hydroxyl groups, while Na , K , Rb and Cs will form octahedral symmetry (Wells, 1962). This is proved by the present experimental results (Table 4), because lithium ions show a drastic effect, while differences between the other cations are not great and exhibit a denitive trend. The setting time of CAC decreases in the following order: Cs . Rb . K . Na .. Li. This order is in agreement with the decrease of ionic radius of the metals. The induction period during the precipitation of CAC hydration products from a supersaturated solution is a reection of the nucleation barrier to the formation of these compounds (Barret et al., 1974). The accelerating effect of lithium has been attributed to removal of this barrier, caused by an initially fast precipitation of lithium hydrometaaluminate (Matusinovic et al., 1994; Rodger and Double, 1984), which acts as a heterogeneous nucleation substrate, promoting the nucleation of the hydration products. The inuence of alkali metal chloride addition on the exural and compressive strength of CAC pastes has been studied. The results of measurements are given in Figures 24. The results of compressive strength measurement at early ages of CAC pastes and CAC pastes prepared with different fractions of lithium chloride are shown in Figure 2. It can be seen that along with rapid setting, lithium salts cause strength development at early ages. The precipitation of lithium hydrometaaluminate is responsible for the rise of compressive strengths of CAC samples at very early ages (t , 10 h) resulting in higher strengths compared

60 50 40 30 20 10 0 0 5 10 t: h 15 20 LiCl w 0050% w 0025% w 0010% CAC

Figure 2. Evolution of compressive strength during early ages of CAC pastes made with different mass fractions of lithium chloride

Compressive strength: MPa

13 12 11 10 9 8 7 6 0 5 10 15 t: d 20 25 30 CAC Li Na K Rb Cs

005%

Figure 3. Effect of alkali metal chlorides on evolution of exural strength of CAC pastes

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Inuence of metal chloride salts on calcium aluminate cement hydration Ukrainczyk, Vrbos and Sipusic

80

Compressive strength: MPa

75 70 65 60 55 50 0 5 10 15 t: d 20 25 30 CAC Li Na K Rb Cs

hydration, which causes a considerable temperature increase of prepared specimens (Banll, 1995; Ukrainczyk and Matusinovic, 2010). Such uncontrolled temperature increase of specimens could also contribute an increase in the amount of the formed C2 AH8 when the lithium ion is added (Matusinovic et al., 1994; Rodger and Double, 1984).
w 005%

Figure 4. Effect of alkali metal chlorides (w 0.05%) on evolution of compressive strength of CAC pastes

to the reference (plain) CAC sample. The increase of the strength is caused by precipitation of lithium hydrometaaluminate, which acts as a heterogeneous nucleation substrate and promotes the nucleation of the calcium aluminate hydrates. After about 15 h the strength of the specimens with the lithium addition is lower than the reference strength. A higher mass fraction of LiCl causes lesser long-term compressive strengths (Figure 2). Based on the setting time results in Table 3 the mass fraction of alkali metal chloride addition of w 0.05% was taken for further research. The inuence of alkali metal chlorides on evolution of exural and compressive strength of CAC pastes is presented in Figures 3 and 4, respectively. It can be seen that all alkali metal salts decrease compressive and exural long-term strengths of CAC, compared to the reference (plain) CAC paste. The extent of this reduction in strength follows the same order as for the setting time reduction: Cs , Rb , K , Na ,, Li (which is in agreement with the order of the ionic radius of the metals). It is worth noting that although the lithium ion exhibits a drastic setting time reduction (Table 3), the corresponding long-term strength reduction (Figures 3 and 4) is only somewhat more pronounced in comparison to other alkali cations. The strength reduction pattern for lithium has a higher reduction effect, while differences between the other cations are not great and exhibit a denitive trend. This is similar, but not as drastic to the setting behaviour. The strength reduction with alkali addition can be attributed to a more rapid nucleation and growth of hydration products because of the smaller crystalline sizes of hydration products and thus smaller surface contact area, as well as to the higher degree of the transformation reactions of the metastable hydration products because of the higher self-heating of the specimens. At ambient temperature metastable hydrates transform to the more stable C3 AH6 and AH3 with a release of water and a consequent higher degree of hydrated CA. This transformation is accelerated by temperature and moist conditions. During the hydration of CAC, a large quantity of total heat is liberated in the rst 24 h of 254

The results of the present study are in agreement with Grifths et al. (1991) who reported that sodium (Na) and potassium (K) act as accelerators (15 mmol/kg). On the other hand, Rodger and Double (1984) indicated that sodium and potassium behave as retarders (25 mmol/kg), while Currell et al. (1987) reported sodium as an accelerating but potassium as a retarding admixture. It has to be noted that Grifths obtained results from conduction calorimetry at carefully controlled conditions of temperature, while Rodger and Double (1984) and Currell et al. (1987) performed semi-adiabatic calorimetric measurements at 22 28C and 18 38C, respectively. Owing to a high sensitivity of setting time variations with temperature, such poorly controlled temperature conditions could explain the confusing results in the literature. Furthermore, in Grifths et al. (1991) and Rodger and Double (1984), the authors did the comparison analysis of the setting behaviour according to the time of maximal heat generation (or temperature) tmax instead of t0 , although the parameter t0 better corresponds to the real initial setting time as obtained by Vicat measurements. Indeed the effect of salt addition may decrease the hydration rate and postpone tmax as a result of the attening and stretching of the shape of the main hydration peak (as discussed in the Transition metals section). Moreover, in different boundary conditions, that is semi-adiabatic (Currell et al., 1987; Rodger and Double, 1984) or semi-isothermal (Grifths et al., 1991), the heat (or temperature) evolution curve is signicantly different, resulting in different tmax values. The setting time of CAC decreases in the following order: Cs . Rb . K . Na .. Li, which correlates with the ionic radius of the metals. To correlate experimental results of the inuence of various cation additions on the CAC (Secar 71) hydration, Murat and Sadok (1991) employed mathematical modelling based on a modication of the expression of nucleation free enthalpy (relying on a hypothesis of homogeneous nucleation), which in the dilute solution approximation leads to the following single equation 1:

ln (rn ) a b=R

where rn is the nucleation rate approximated to (1/t0 ), where t0 is the experimentally determined setting time, R is the ionic radius and a and b are tting parameters. This model (Equation 1) has been previously veried on experimental results of calcium sulfate hydration (anhydrite and hemihydrate). For the alkali metals we have investigated a correlation according to Equation 1. The results are shown in Figure 5. The lithium ion

Advances in Cement Research Volume 24 Issue 5

Inuence of metal chloride salts on calcium aluminate cement hydration Ukrainczyk, Vrbos and Sipusic

is omitted from the regression analysis because of its drastically different behaviour, as already detailed above. As expected, from Figure 5 it is obvious that constant mass concentration is not an adequate parameter for the analysis. For w 0.05% the corresponding molar concentrations for lithium (Li), potassium (K), sodium (Na), rubidium (Rb) and caesium (Cs) are 11.8, 8.6, 6.7, 4.1 and 3.0 mmol/kg, respectively. This signicant increase of molar concentrations from the reference concentration of 3.0 mmol/kg results in further/higher increase of the setting time. For a constant molar concentration (3 mmol/kg) the regression analyses resulted in a reasonably good correlation coefcient (R 0.92927). Alkaline earth metals Measurements of the initial and nal setting time parameters, that is ti and tf , respectively, was obtained as described in the Setting time measurement section. In order to compare the results, a range of the prepared mass concentrations (fractions relative to weight of cement) were transformed to molar concentrations, as shown in Table 5. The effect of a range of molar concentrations from 4.8 to 525 mmol/kg on the setting time is presented in Figure 6. It can be observed that lower concentrations (0.1% or

400

Setting time: min

300 Mg Ca Sr Ba

200

100

0 0 100 200 300 : mmol/kg CAC 400 500

Figure 6. Inuence of alkaline earth metal chloride addition on the initial setting time of CAC pastes (horizontal line: value for plain CAC)

30 25 20 15 w 005% 3 mmol/kg Linear fit Li

ln(1/ti)

10 05 0 05 10 15 Cs

ln(1/ti) 136 R 092927 K

24/r

Rb

Na CAC

0006

0008

0010 1/r: pm 1

0012

0014

up to 10.5 mmol/kg, according to Table 5) resulted in a retardation of the setting behaviour. Addition of 0.5% of salts for calcium (Ca) and strontium (Sr) brought about setting times close to that in the absence of any admixture, while barium (Ba) and magnesium (Mg) showed signicant acceleration. A further increase of admixture concentration results in a dramatic acceleration of the setting time in the presence of any of the four salts. Furthermore, from Figure 6 it can be seen that calcium chloride (CaCl2 ) has the strongest acceleration effect in comparison with the other alkaline earth metal chlorides, while magnesium chloride (MgCl2 ) has the weakest acceleration effect. The highest concentration (w 5%) of calcium (Ca) and strontium (Sr) resulted in a ash set during mixing. As can be seen in Table 5 the addition of a constant mass fraction of salts results in different molar concentrations that complicate a further detailed analysis. Unfortunately, the present experiments on the inuence of alkaline earth metal chlorides were conducted with a constant mass concentration, not xing the molar concentrations. The results presented here are compared with the available literature results obtained on Lafarge iron-rich CACs, focusing on 5.0%

Figure 5. Investigation of the correlation according to Equation 1; ti is measure in hours (horizontal line: value for plain CAC)

0.1%

0.5%

1.0% : mmol/kg

2.0%

MgCl2 3 6H2 O CaCl2 SrCl2 3 6H2 O BaCl2 3 2H2 O

10.50 9.01 6.31 4.80

52.52 45.05 31.54 24.01

105.03 90.11 63.08 48.02

210.06 180.21 126.17 96.05

525.15 450.53 315.42 240.12

Table 5. Calculated molar concentrations in mmol/kg of CAC for a corresponding mass fraction

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Inuence of metal chloride salts on calcium aluminate cement hydration Ukrainczyk, Vrbos and Sipusic

the range of concentrations from 15 to 25 mmol/kg in Figure 6 that correspond to the literature experimental conditions (which are summarised in the introduction). In agreement with the nding of the present study, calcium (Ca) is reported by all three groups of researchers (Currell et al., 1987; Grifths et al., 1991; Rodger and Double, 1984) to act as a retarder. The present studys results also conrm the different behaviours of strontium (Sr) and barium (Ba) ions as reported by Rodger and Double (1984). The differences in the literature regarding the effect of alkaline earth metal chlorides could be attributed to the change of the set behaviour inuence (i.e. acceleration or retardation) with the molar concentration, as well as sensitivity to different chemical compositions of the similar iron-rich cements investigated, temperature of hydration and method of obtaining the setting parameters. Moreover, it is interesting to compare the present studys results to the literature results obtained on a completely different class of CAC, a pure CAC Secar 71 (produced by Lafarge, that has a high aluminium oxide (Al2 O3 ) content of about 70%). Nilforoushan and Sharp (1995) reported an inverted (opposite) trend of the results in Figure 6, that is contrary to the present ndings. They showed that alkaline earth metal additions in low concentrations (12.5 mmol/kg and 25 mmol/kg) exhibit acceleration of the setting, and signicant retardation at higher concentrations (from 50 mmol/kg to 250 mmol/kg). Moreover, Murat and Sadok (1991) reported that all chloride metal salts (mono-, bi-, tri- and tetra-valent) have an accelerating effect on the setting of Secar 71, which also differs from most other studies on iron-rich CACs as summarised in the introduction. Although the inuence of additions on setting behaviour of these two different classes of CAC has been compared in the literature, resting on the hypothesis of the same hydration mechanism of CA mineral, care should be taken in this interpretation because they differ substantially in their properties, principally chemical and mineralogical composition. Refractory Secar 71 CAC, produced by Lafarge, has an aluminium oxide (Al2 O3 ) content of about 70%, resulting in CA and CA2 as the main mineral phases with no C12 A7 , C4 AF and C2 S. The results of the current study have shown that the inuence of alkaline earth metal chlorides additions on setting behaviour of iron-rich CAC and refractory Secar 71 CAC is completely different, with an opposite effect of salts concentration on setting behaviour. This suggests that the hydration mechanism of the two CACs may be quite different. This difference may be principally explained by the C/A ratio of the liquid phase during the nucleation period. The dissolution of the pure main mineral CA shows the C/A ratio to be in the range 1.051.10 (Fujii et al., 1986; Nikushchenko et al., 1973) thereby inevitably initiating the precipitation of AH3 gel. Even slight amounts of C12 A7 or CA2 that accompany CA in the commercial cement composition as separated phases induce a variation of the C/A ratio in the liquid phase. It is known that the presence of small quantities of C12 A7 (in iron-rich CAC) or CA2 (in Secar 71) inuence the duration of the induction period: C12 A7 accelerates the nucleation, whereas CA2 retards it. This has been 256

shown by hydrating a series of synthesised CA samples prepared with C/A ratios ranging from 0.96 to 1.04 (Galtier and Guilhot, 1984). The dissolution of the pure C12 A7 exhibits a C/A ratio of exactly 1.71, showing unambiguously the congruency of its dissolution. Upon hydration of CA2 , large amounts of AH3 gel are produced (Edmonds and Majumdar, 1989) as a rst hydration product. Later, when the lime concentration reaches a sufcient level, C2 AH8 precipitates coinciding with an acceleration of the hydration reaction rate. Thus, the chemical composition of cement inuences the change of the C/A ratio in the liquid phase. With an increasing C/A ratio the length of the induction period diminishes. Because alkaline earth metal cations bear the same charge they behave in a chemically similar way, thus the addition of alkaline earth metal salt increases apparent calcium concentration, thus modifying C/A ratio in the solution. Increasing the C/A ratio of iron-rich CAC induces the formation of AFm and AFt phases that may protect the cement grains surface from dissolution and results in the deceleration of the hydration. The mass concentration of w 1% was chosen to investigate the inuence of alkaline earth metal salt additions on the exural and compressive strength of CAC pastes. The results of measurements are presented in Figures 7 and 8. Alkaline earth metal salts decrease compressive and exural long-term strengths of CAC, compared to the reference (plain) CAC paste. Interestingly, although CaCl2 (with the second highest molar concentration, Table 5) results in the strongest acceleration of the initial setting time (t0 69.5 min) the compressive and exural strengths exhibit the lowest reduction from the reference ones (with no admixtures). On the other hand, addition of 1% magnesium chloride (MgCl2 ) with the highest corresponding molar concentration (Table 5) results in a much lower acceleration of the setting time (t0 163.0 min) but higher strength reduction than calcium chloride (CaCl2 ). Moreover, strontium chloride (SrCl2 ) and barium chloride (BaCl2 ) (with the smallest molar concentrations) show no signicant acceleration effect (Figures 7 and 8)
125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 0 5 10 15 t: days

Flexural strength: MPa

CAC Mg Ca Sr Ba 20

1%

25

30

Figure 7. Effect of alkaline earth metal chlorides (w 1%) on evolution of exural strength of CAC pastes

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90 85

34 32 30 28 tmax tf

Compressive strength: MPa

80 75 70 65 60 55 50 45 0 5 10 15 t: days 20 25 30 CAC Mg Ca Sr Ba w 1%

T: C

26 24 22 20 0 2

Inflection point t0 4 6 8 10 12 14 16 18 20 22 24 t: h

Figure 8. Effect of alkaline earth metal chlorides (w 1 %) on evolution of compressive strength of CAC pastes

Figure 9. Temperature evolution of specimen during standard Vicat method measurement

but exhibit the highest strength reduction (Figures 7 and 8). These results indicate the role of the foreign cations, which can replace the calcium in the hydration products and/or even form novel hydration products that change the rate of hydration development and inuence strength development. Further research is needed to investigate the nature of the hydration products formed (e.g. on the hydration of the pure phases with foreign cation additions). Temperature evolution and setting time measurements The rapid hydration and the resulting heat evolution allows an accurate determination of both the induction time t0 and the time tmax of the maximum temperature (or heat generation) hydration peak. Setting can be attributed to the interlocking of the hydration products when their formation takes place to an appreciable extent. Unlike calorimetry or temperature rise measurements, the Vicat initial setting time is signicantly affected by the water-tocement ratio attributable to the consistency of the paste being tested. This reects the fact that the setting time is an arbitrarily dened parameter. In a more uid paste, a longer time is needed to reach the required resistance to penetration. As suggested by Stegemann and Buenfeld (2001) preferable techniques for measuring setting time, although less traditional and indirect, are isothermal calorimetry, temperature rise and solution conductivity measurements. In this paper times of initial, t0 , and nal, tf , sets for experimental series on transition metals were established from the obtained timetemperature curves, as illustrated in Figure 9. Initial set is acquired from the intersection of two straight lines (Bushnell-Watson and Sharp, 1986): one tted through the induction period of the curve and the other tted through the inection point of the rising slope of the main peak. The nal set was approximated as the point of maximal heat generation. In order to conduct the comparison of the values of setting time parameters obtained by Vicat method and temperature rise measurements, the temperature of the specimen in a Vicat mould was

measured as described in the CAC temperature evolution measurement set-up section. The experiment on plain cement paste (without admixtures) was repeated ve times. It was found that the difference between the initial setting time obtained by the two methods, (ti t0 ) was only 1.2 min 0.6 min. This validates the further use of the employed alternative method to obtain accurate values of the setting time parameters. Interestingly, the time of nal set tf was found to be 9 min 1.5 min below the point of inection (Figure 9). An example of a temperature evolution of a specimen during simultaneous standard Vicat method measurement is shown in Figure 9. The inuence of the sample mass and heat transfer boundary conditions can be analysed by comparing Figures 9 and 10 (for the plain CAC). After moulding the cement paste and xing of the thermocouple within a few minutes, a decrease of temperature is occurring owing to the dissipation of the heat generated by the initial wetting of cement, chemical dissolution
CAC 23

Co Mn Cu

(Me2 )

10 mmol/kg CAC CAC Co Mn Cu Zn

22

T: C

Zn 21

20 5 10 15 t: h 20 25

Figure 10. Effect of transition metal chlorides on the temperature evolution of CAC, 10 mmol/kg of CAC

257

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and partial hydration before reaching the induction period with very small heat generation (Banll, 1995; Ukrainczyk and Matusinovic, 2010). The hydration of CAC at temperatures below ,208C shows the high inuence of water-to-cement ratio on hydration rate and the obtained hydration degree due to the high stoichiometric water requirement for the formation of metastable hydration products (Bensted, 2002; Fryda et al., 2001; Ukrainczyk and Matusinovic, 2010). The cement hydration is incomplete if there is not enough water for stoichiometric hydration, so the hydration rate decreases because of the free water consumption and reaches zero value upon water insufciency. In non-isothermal conditions (Figure 9) the temperature increase is higher due to lower heat loss to the environment. The shoulder in Figure 9 before reaching tmax is a consequence of the signicant commencement of the transformation reactions (Fryda et al., 2001). As the rate of transformation reactions of metastable products to the stable C3 AH6 and AH3 is signicantly increasing with the temperature, the associated free water liberation allows further reaction of cement and thus increases the hydration rate (Bensted, 2002; Fryda et al., 2001; Ukrainczyk and Matusinovic, 2010). This also explains why the time of maximal temperature rise, tmax , is reached signicantly later after the onset of the acceleration period in Figure 9 than in Figure 10, but with a faster diminution of the hydration rate after the maximum at tmax : The high temperature sensitivity of the setting time measurement of CACs is not adequately addressed in most of the literature. One point is the poor control of the starting temperature (e.g. Currell et al., 1987; Rodger and Double, 1984), probably the result of following the Vicat standard procedure, which is written for measurements on a PC that does not have such pronounced temperature sensitivity as CAC. A second point is that, owing to a rapid hydration of CAC with a corresponding high heat generation effect (about 20 mW/g in isothermal conditions (Banll, 1995; Ukrainczyk and Matusinovic, 2010)), the temperature evolution of the material strongly depends on the heat transfer boundary conditions around the testing specimen. In different boundary conditions, that is semi-adiabatic as in work by Currell et al. (1987) or Rodger and Double (1984) or semi-isothermal as in work by Grifths et al. (1991) or Murat and Sadok (1991), the heat (or temperature) evolution curve is signicantly different, which could result in signicantly different tmax values. Some authors (Currell et al., 1987; Grifths et al., 1991; Rodger and Double, 1984) did the comparison analysis of the setting behaviour according to the time of maximal heat generation (or temperature) tmax instead of t0 , although parameter t0 better corresponds to the real initial setting time as obtained by Vicat measurements. For an isoperibol calorimeter, the evolved heat in time t equals the accumulated heat in the calorimeter (that results in the increase of the calorimeter temperature) and the heat loss to the surroundings (a constant-temperature environment). Conduction (semi-isothermal) calorimeters have small temperature rise of the samples, whereas semi-adiabatic calorimeters have small heat transfer to the surroundings. 258

Transition metals To the best of the current authors knowledge, Rodger and Double (1984) are the only researchers who investigated the effect of transition metal chlorides on iron-rich CAC (manufactured by Lafarge). They reported the time of maximum temperature rise of CAC samples (w/c 0.5 with 25 mmol of salt per kg of CAC) in semi-adiabatic conditions. The present authors analysed the results of Rodger and Double against the added metallic atomic number, as depicted in Figure 11. A well-dened trend can be observed in the inuence of transition metals on setting behaviour. It is well known that various trends are observed when studying chemical reactions or some physical properties within the transition metal group. For example, enthalpy change accompanying solvation of cations by water molecules or melting point of pure metals, and so on. The cause of such behaviour is qualitatively explained by the gradual lling of the 3d-orbital by electrons taking into account Hunds rule of maximum multiplicity. Interestingly, the regularity of the setting times observed in Figure 11 follows the same principle. In order to clarify this nding, previously not addressed in the literature, part of this paper is devoted to investigating further the inuence of transition metals, in the form of chloride salts, on the hydration of similar (same class) CAC from a different manufacturer (namely, Istra cement, Calucem). The equilibrium between precipitated and soluble species is in fact dependent on the acid/base properties of the precipitate. The present authors argue that the acid/base properties of the precipitate cause the observed regularity of setting times plotted against atomic number in Figure 11. The acidity of the precipitate can be described by the following chemical reaction in base media 2:

MeOH2 cr: OH aq: $ MeOH3 aq:

pKa curve t(Tmax) curve 1000 Zn2 5 Cu 800 Mn 600 Fe2 400 25 26 27 28 Atomic number, Z 29 Co
2 2 2

t(Tmax): min

Ni2 CAC

2 30

Figure 11. Variation of time of maximum temperature rise of CAC samples (see text for details) and acidity of crystalline Me(OH)2 quantied by pKa value, plotted against the added cations atomic number

pKa

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Inuence of metal chloride salts on calcium aluminate cement hydration Ukrainczyk, Vrbos and Sipusic

Setting time: min

The values of acidity constants, pKa , are obtained from thermodynamic data (Shkolnikov, 2005) and plotted in Figure 11. These values for pKa correspond to the fully crystalline hydroxide precipitate. The observed discrepancy for copper and zinc could be explained by the fact that freshly precipitated amorphous hydroxide has higher solubility and is therefore expected to be more acidic. Aluminium also participates in this type of acid/base equilibrium according to the following reaction 3:

700 Initial setting time, ti 600 tmax

500 Cu2 400 Mn2 Co2

Zn2

AlOH3 cr: OH $ AlOH4 aq:

300

The reaction in Equation 3 has pKa 5.9 (Nordstrom and May, 1989). Calcium hydroxide has no observable acidic properties. By comparing the trends of the setting time and pKa change plotted against atomic number (Figure 11) it can be concluded that they agree only qualitatively. Generally, the discrepancies in quantitative agreement can be ascribed to the complexity of the real chemistry behind the studied process of CAC hydration. Overall, the suggested explanation is that the more the acid/base properties (real pKa values) of transition metal precipitates deviate from the aluminum hydroxide; the setting time of the CAC is more prolonged. This concept of acid/base reactions and the inuence on the setting time of calcium aluminate cement is also corroborated by Mohmel and Gessner (1997), who showed that acid/base properties of corundum ller signicantly inuence the setting of CAC. The inuence of transition metal chloride salts on hydration was investigated by measuring the temperature evolution of CAC pastes (as described in the CAC temperature evolution measurement section). Results of temperature evolution measurements for pastes prepared with (Me2 ) 10 mmol/kg are shown in Figure 10. No signicant temperature rise is observed during the induction period owing to a small and constant rate of heat generation (about 0.3 mW/g (Banll, 1995; Ukrainczyk and Matusinovic, 2010)). The induction period is followed by the onset of the accelerated stage of reaction due to massive precipitation of hydrates. The maximal temperature rise is reached in only a few hours after the onset of the accelerated stage. With the addition of the transition metal chlorides the main hydration peak of the temperature evolution curve becomes atter and longer (with a lower value of maximal temperature at tmax ) in the following order: Co , Mn , Cu , Zn. This attening and stretching effect of the main hydration peak supports the notion of slower growth and crystallisation of hydration products. The effect of various transition metal chlorides on the setting time of CAC is investigated for two concentrations, 100 mmol/kg and 10 mmol/kg. The concentration of 100 mmol/kg showed no setting behaviour within 30 h of hydration. The inuence of transition metal chloride addition ( 10 mmol/kg) on the setting time of CAC pastes is depicted in Figure 12. The results are plotted against the atomic number. It is obvious that all investigated transition metal chlorides act as retarders, which is in accord with results obtained by Rodger and Double (1984). The retardation effect is higher for

200 25 26 27 28 Atomic number, Z 29 30

Figure 12. Inuence of transition metal chloride addition ( 10 mmol/kg) on the setting time of CAC pastes (horizontal lines: values for plain CAC)

higher concentrations. In agreement with the nding in Figure 11, the experimental data from the present study reproduced the dened trend of the change of setting times against the added cations atomic number well. A comparison of the obtained results with the literature (Rodger and Double, 1984) is depicted in Figure 13. The results are plotted against the reciprocal values of ionic radii (Shannon, 1976) in order to test the validity of Equation 1, which relies on an assumption of homogeneous nucleation (Murat and Sadok, 1991). The results of Rodger and Double have lower (more negative) values of ordinate, which corresponds to the longer absolute setting time values (compare Figures 10 and 11), primarily owing to the much lower water-to-cement mass ratio employed in this investigation (i.e. w/c 0.25 as opposed to 0.50). The translation of the results shows very good agreement of the trend between the present results and the results obtained previously by Rodger and Double (1984). It is clear that the
12 14 16 18 Co Ni Fe

ln(1/t0)

20 22 24 26 28 30 Zn

Mn Cu Current paper Rodger and Double (1984)

00135 00140 00145 00150 00155 00160 00165 1/r: pm

1

Figure 13. Comparison of results obtained in the present study with those presented in the literature; ti is measured in hours

259

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experimental data signicantly deviate from the model in Equation 1.

Compressive strength: MPa

85 80 75 70 65 60 55 50 45 25 26 27 28 Atomic number, Z 29 30 Mn2 28 days 7 days 1 day Zn2 Co2 Cu2 CAC

On the other hand, on the Secar 71 as a different class of CAC, Murat and Sadok (1991) reported that transition metal chlorides have an accelerating effect. Again, as discussed in the Earth alkali metals section, the inuence of transition metal chloride additions on setting behaviour of iron-rich CAC and refractory Secar 71 CAC is shown to be completely different. This suggests that the hydration mechanisms of these two classes of CAC are signicantly different (as discussed in the Earth alkali metals section). Murat and Sadok (1991) have explained the acceleration effect by an hypothesis of a heterogeneous nucleation process, the nuclei formed being grains of metallic hydroxide (or hydrated aluminates for Li and Ni2 ions in the form of double-layer hydroxide phases) that lead to an increase of the nucleation rate. In the present case of iron-rich CAC, the retardation effect may be explained by the massive precipitation of protective gel (amorphous hydroxides and/or double-layer hydroxide phases) coatings on the phase boundary surface of cement grains (Rashid and Turrillas, 1997), which block hydrolysis and inhibit growth of the crystalline hydration products. The effect of attening and stretching of the main hydration peaks observed in Figure 10 could thus be explained by a formation of larger quantities of, and/or more impermeable, gel coatings that hinder crystallisation and growth of the hydration products. The inuence of transition metal salt additions on the exural and compressive strength of CAC pastes was studied. The results of measurements of exural and compressive strength at 1, 7 and 28 days are presented in Figures 14 and 15, respectively. Horizontal lines represent experimental values of strength for the plain CAC, which are increasing with age. Generally, the addition of transition metal salts decreases compressive and exural strengths of CAC, compared to the reference (plain) CAC paste.
14 13 CAC Co2 28 days 7 days 1 day

Figure 15. Effect of transition metal chlorides ( 10 mmol/kg) on evolution of compressive strength of CAC pastes (horizontal lines: values for plain CAC)

When comparing Figures 14 and 15 with Figure 12 it can be concluded that the magnitude of strength reduction for all tested ages follows the order observed for the setting time retardation. For example, the cobalt (Co) sample, which has the setting time the closest to the plain CAC, achieves the smallest reduction in strength. On the contrary, the zinc (Zn) addition results in the highest retardation of the setting time and exhibits the highest reduction in strength. Integration of the temperature change evolution curve (curves shown in Figure 10 were subtracted by 208C before integration) gives an approximation of a relative amount of achieved degree of hydration. It was observed that the relative degree of hydration after 24 h has a tendency to lower in the following order: none . Mn . Co . Cu . Zn. This order is in agreement with the magnitude of the strength reduction in Figures 14 and 15. Thus, the strength reduction may be primarily attributed to the lower hydration degree achieved owing to the retardation of the hydration reaction rate (Figure 10).

Flexural strength: MPa

12 11 10 9 8 7 6 5 25 26 27 28 Atomic number, Z 29 Cu2 Mn2

Conclusions
Addition of alkali metal salts accelerates the setting time of CAC in the following order: Cs , Rb , K , Na ,, Li. This order is in agreement with the increase of ionic radius of the metals. A reasonable correlation was observed between setting time and the ionic radius of alkali metals, excluding lithium (Li). The accelerating effect of alkali metals has been attributed to the removal of the nucleation barrier, through an initially fast precipitation of alkali metal hydration products (e.g. lithium hydrometaaluminate) that act as a heterogeneous nucleation substrate, promoting the nucleation of the CAC hydration products. The lithium has a much greater effect on the setting time than other alkali cations because of its ability to form tetrahedral symmetry while other alkali cations form octahedral symmetry. Along with rapid setting, small quantities of lithium salts cause

Zn2

30

Figure 14. Effect of transition metal chlorides ( 10 mmol/kg) on evolution of exural strength of CAC pastes (horizontal lines: values for plain CAC).

260

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strength development of CAC at early ages, so they can be used for preparation of rapid hardening cement-based materials for example, in rapid repair mortars. Alkali metal salts deteriorate/ reduce compressive and exural long-term strengths of CAC. The extent of strength reduction followed the same order as for the setting time reduction. Effect of alkaline earth metal salts on setting behaviour depends on the amount of addition. Low concentrations (0.1%) resulted in a retardation of the setting behaviour. A further increase of admixture concentration results in a dramatic acceleration of the setting time. Calcium addition results in the strongest acceleration of the initial setting time, while the compressive and exural strengths exhibit the lowest reduction from the reference material. Thus the change in the nucleation rate and the corresponding deterioration of the strengths can be attributed to the role of the foreign cations, which can replace the calcium in the hydration products and/or form novel hydration products. A simple method of analysing CAC hydration based on the measurement of temperature rise of cement pastes was described. Setting times were established from the timetemperature curves obtained. The results of the setting time obtained from the measured temperature evolution of cement pastes were compared to the standard Vicat needle measurements. The difference between the initial setting time obtained by the two methods is only 1.2 min 0.6 min. This validates the further use of the employed alternative method to obtain accurate values for the initial setting time parameter. The effects of the sample mass and heat transfer boundary conditions during setting time measurements were analysed. With the addition of the transition metal chlorides the main hydration peak of the temperature evolution curve becomes atter and longer, and the setting is retarded in the following order: Co , Mn , Cu , Zn. The retardation effect is higher for higher concentrations. A well-dened trend, which was observed when plotting the results of setting times against added cations atomic number, was related to the change in the acid/base properties of the precipitate. The retardation effect may be explained by the precipitation of protective gel (amorphous) coatings on the phase boundary surface of cement grains, which block hydrolysis and inhibit growth of the crystalline hydration products. Magnitude of strength reduction for all tested ages follows the order observed for the setting time retardation. The strength reduction may be primarily attributed to the lower hydration degree achieved due to the retardation of the hydration reaction rate. The inuence of alkaline earth and transition metal chlorides additions on setting behaviour of iron-rich CAC and refractory Secar 71 CAC is shown to be opposite in nature. This suggests that the hydration mechanisms of these two classes of CAC are signicantly different. It is recommended that for further investigations of the admix-

tures a constant molar concentration (represented in added mols per mass of cement) should be used. This will enable a better comparison of the results among researchers, even when mixtures are prepared with different water-to-cement ratios.

Acknowledgement
The authors acknowledge support from the Croatian Ministry of Science, Education and Sports under projects no. 125-12529702983 Development of hydration process model.

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