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Advances in Cement Research, 2012, 24(5), 249–262 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
Inﬂuence of metal chloride salts on calcium aluminate cement hydration
Post-doctoral Researcher, Faculty of Chemical Engineering and Technology, University of Zagreb, Zagreb, Croatia
ˇ ˇ ´ Juraj Sipusic
Associate Professor, Faculty of Chemical Engineering and Technology, University of Zagreb, Zagreb, Croatia
Assistant Professor, Faculty of Chemical Engineering and Technology, University of Zagreb, Zagreb, Croatia
In this paper the inﬂuence 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.
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 ) ﬁtting 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 coefﬁcient nucleation rate (sÀ1 ) silica (SiO2 ) temperature (8C) time (h) time of initial setting obtained by Vicat measurement time of ﬁnal 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)
The duration of the suitable workability of cement-based materials during placement is deﬁned by setting time. The use of additives to modify the properties of cement-based materials for each speciﬁc application is a subject of great practical and ﬁnancial interest. From practice, it is known that even small amounts of different organic and inorganic compounds have a pronounced inﬂuence 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 ﬂoors, 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 ¼ calcium oxide (CaO), A ¼ aluminium oxide (Al2 O3 ), F ¼ iron oxide (Fe2 O3 ), S ¼ silica (SiO2 ), 249
at low concentrations. Murat and Sadok (1991) considered the role of foreign cations in the hydration kinetics of refractory CAC (Secar 71. The effects on the setting time may be summarised as follows: Liþ . Mg2þ . less for CAC than for PC hydration.27 in the presence of many additives with different concentrations. they reported the following order at the various temperatures: Mg2þ . and as a retarder.g. permeability increase and loss of strength. Sr2þ : Grifﬁths et al. 2010). At 208C. 208C) Currell et al. At 288C and 368C. (1987) investigated the setting of iron-rich CAC 250 (manufactured by Lafarge. produced by Lafarge.. For alkali chlorides sodium (Na) and potassium (K) are reported to act as both retarders and accelerators. respectively. Mg2þ . Ba2þ . Upon water addition to cement a sharp increase of the pH of the water solution occurs. At 128C all of the alkaline earth metal chlorides investigated exhibited retardation of setting. K þ . namely Lafarge Ciment Fondu. tri.. For alkaline earth metal chlorides magnesium (Mg) acts as an accelerator. 2001). thus opening an attractive route for heavy metal waste stabilisation. Vrbos and Sipusic H ¼ water (H2 O)). 2007) transform to the more stable C3 AH6 and AH3 with consequent material porosity. (1987). ˜T . as detailed below. Naþ . Mg2þ . but other compounds may also participate in the hardening process. Ca2þ at 158C.. The inﬂuence of the particular additive on setting behaviour of CAC is generally not so well understood and contradictorily statements can be found in the literature. the authors have studied the inﬂuence of alkali.. Sr2þ . none . has been compared in the literature. A similar chemical composition of CAC is used in the present work (with 10% F (iron oxide)) but from a different producer. K þ .4) at different temperatures in the presence of 15 mmol/kg metal chlorides and sulfates. Naþ . yielding morphologically different hydration products at different temperatures of hydration. none . Naþ . Ba2þ at 208C and 308C. none . In the present paper. the more so with increasing concentration of the admixture. Rodger and Double (1984) studied the inﬂuence of alkali. similar chemical composition as in the present work except for somewhat lower iron oxide content at 10%) pastes (w/c ¼ 0. care should be taken because they differ substantially in their properties (principally chemical and mineralogical composition). . Using the time corresponding to the maximal rate of heat generation to compare the setting behaviour in the presence of chlorides. 1991. 1987.5–250 mmol/kg) of alkaline earth metal chloride salts at different temperatures. They concluded that all chlorides metal salts (mono-. K þ . is also of interest in stabilisation of hazardous waste containing potentially soluble heavy metals (Jantzen et al. according to Currell et al. as two different classes of CACs. none .and tetravalent) have an accelerating effect on the set of Secar 71. mainly with respect to the dissolution of anhydrous cement. The admixtures can interfere with hydration of cement in a variety of ways. The literature regarding the inﬂuence of alkali and alkaline earth metal chlorides on the hydration of iron-rich CAC is confusing. 1008C). This result differs from most other studies summarised above. ´ The hydration of CAC is highly temperature dependent. The transformation is accelerated by temperature and moisture availability for the dissolution and re-precipitation processes to take place (Mangabhai and Glasser. Nilforoushan and Sharp (1995) investigated the setting of Secar 71 with a range of concentrations (12. the measurement technique employed and the conditions of hydration. Ca2þ : Furthermore. 2008). ˜T . but they acted as retarders at higher concentrations. Rodger and Double reported that all transition metals chloride salts have a retarding effect on the set of CAC. bi-. especially in long-term strength development (Ukrainczyk. which causes precipitation of highly insoluble metal oxide–hydroxide. Ca2þ . Lastly. according to Rodger and Double (1984). Using a semi-adiabatic calorimeter (T ¼ 18 Æ 28C. At ambient temperature metastabile hydrates. Along with rapid setting. A number of different mechanisms have been suggested (e. The summarised effect on setting time is in the following series: Liþ . Ba2þ . 1984) to explain the action of set regulators on cement hydration. The above-stated conﬂicting results can be summarised as follows. alkaline earth and transition metal chlorides additions on setting behaviour as well as strength development of commercial iron-rich CAC. Part of the controversy could arise primarily from differences in the cement composition. that has an aluminium oxide (Al2 O3 ) content of about 70%). which were reported to act differently. Caþ . 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. (1991) studied the setting of iron-rich CAC (Lafarge. which increased with increasing concentration of the admixture. and the nucleation and precipitation processes for the main hydration products. with a relatively low iron oxide content of 6% compared with the CAC used in the present study) pastes with a w/c ¼ 0. Ukrainczyk and Matusinovic. they were shown to accelerate the setting. 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. Naþ .5 by measuring the maximum temperature rise in a semi-adiabatic calorimeter (T ¼ 22 Æ 28C.. Although the inﬂuence of admixtures on setting behaviour of iron-rich and refractory Secar 71 CACs. some metal salts result in the rapid strength development of CACs at very early ages. that is as retarder and accelerator. 2010. as well as sea water. Currell et al. Only Rodger and Double (1984) investigated the effect of both strontium (Sr) and barium (Ba). they retarded the setting. Murat and Sadok. so they are advantageously used for rapid repair works of highways and airport runways (Justnes. K þ . The inﬂuence of metal salts on cement hydration. particularly setting time and compressive strengths. 2010).Advances in Cement Research Volume 24 Issue 5 Inﬂuence of metal chloride salts on calcium aluminate cement hydration ˇ ˇ ´ Ukrainczyk. CAH10 and C2 AH8 (Ukrainczyk et al. Rodger and Double.
19 3.a. Mechanical properties Cement paste specimens (40 3 40 3 160 mm) were prepared according to ASTM C 109 (with a standard consistency). respectively.30 Na2 O 0.50. SrCl2 6H2 O and i BaCl2 2H2 O.7 mm thick. 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. Temperature evolution measurements were also performed simultaneously on the specimens tested for setting time.05 n. cm2 /g Speciﬁc gravity: g/cm3 3. This was designed by ﬁxing a thin (1. 1. dissolved in freshly deionised water before mixing with the cement. E and T.40 ìm: % Blaine.17 FeO 2. NaCl.18 K2 O 0. Transition metal salts. Pula. and â-C2 S as minor compounds. Specimens were tested at laboratory conditions of T ¼ 20 Æ 28C.a. 50 mm high and 0.50% (0.3 mm) wooden support through the axis of the paste in the mould.10.240 0.12 Al2 O3 38. Chemical composition of investigated CAC Sample . Specimens were carefully sealed with lids and polyvinyl chloride electrical insulation tape and placed vertically in the temperature-controlled water bath T ¼ 208C (Æ0.0 and 5.90 ìm: % . KCl.3 Table 1. the cement and water components were left to reach thermal equilibrium (overnight) in a sealed container placed in a thermostat. that is through the axis at half-thickness of the specimen. Physical properties of investigated CAC 251 . CAC temperature evolution measurement set-up The specimens were cast in high-density polyethylene containers with inner diameter 2R ¼ 31 mm. CoCl2 6H2 O.2 mm thick with TiO2 1.00025 to 0.19 3. Alkaline earth metal salts: MgCl2 6H2 O.0%.7 13. Physical properties of the cement are given in Table 2.a. 0. 2.2 39. To prepare the samples of pastes the additives were weighed into deionised water according to a speciﬁed concentration and then mixed with cement. Alkali metal salts.90 4. gehlenite. continuously applying vibrations in order to minimise air entrapment. CaCl2 .39 11. C12 A7 . The thermocouple measuring end was placed exactly at the centre of the container (r ¼ 0 and z ¼ h/2 as shown in Figure 1). using a standard Vicat apparatus. 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).9 4. The high-density polyethylene container was fully ﬁlled with the cement paste (with a standard consistency).10 40.50 80. The main compounds are CA and ferrite phase (C4 AF– C6 AF2 ).71 80. RbCl and CsCl. The experiments used a standard consistency CAC paste. the thermocouple sensing end was placed at the weight centre.06–118 mmol/kg). 1.Advances in Cement Research Volume 24 Issue 5 Inﬂuence of metal chloride salts on calcium aluminate cement hydration ˇ ˇ ´ Ukrainczyk.14 0.240 0. Bending and compression tests at different ages were done according to EN 1015-11.90 n. alkaline earth and transition metal chlorides was studied on cement samples A. The salts used as additives were commercial Analar grade reagents. CuCl2 2H2 O and ZnCl2 . were mixed with a mass fraction (relative to weight of cement) of 0. MnCl2 H2 O. The effect of alkali.8 97.78 Fe2 O3 14. with mayenite.10 80. This was done by immersing a thin (1.90 3407 3421 3563 Table 2.46 SiO2 4. Before mixing. were studied at 10 and 100 mmol/kg of cement. wooden support at the axis of the container. made up from non-absorbent plastic with a glass base plate) was ﬁlled with the cement paste. Croatia.05% and molar concentration of 3 mmol/kg of cement.16 0.80 MgO 0.0.17 0. Sample A E T CaO 37.3 mm).20 Setting time: min Initial 264 300 209 Final 279 322 236 Water-to-cement mass ratio of standard consistency 0. as given in Table 2. and LiCl from 0.76 3.47 39. were mixed with mass ratios (relative to weight of cement) of 0.17 Sum 99.43 1.42 Setting time measurement The setting time was determined using the standard Vicat needle method carried out according to EN 196-3. 0. C2 AS.038C). The K-type thermocouples used were 0. After the Vicat mould (DIN standardised truncated conical form: 75 mm in diameter at the base.250 A E T 3. Three specimens were tested for each age.4 100.70 3. 65 mm at the top and 40 mm high.91 SO3 0.3 2.20 n. The cement has the oxide mass fraction composition listed in Table 1.13 0.0 37. 0.
which corresponds to a molar concentration of ª ¼ 0. Schematic diagram of the CAC paste temperature evolution measurement set-up grounded. w (LiCl): % 0 0. With the mass fraction of 0.Advances in Cement Research Volume 24 Issue 5 Inﬂuence of metal chloride salts on calcium aluminate cement hydration ˇ ˇ ´ Ukrainczyk. both of the setting time parameters continuously decrease. is generally believed to occur through initial dissolution.18 1. that is ti and tf respectively.8 23. I denotes setting of the CAC immediately after addition of lithium chloride Table 3.06 mmol/kg. The data show that lithium chloride accelerates the setting time of CAC even for very low additions of only w ¼ 2.36 5.050 0.010 0. It is obvious that lithium metal shows a drastic effect of acceleration in comparison to other alkali metals. principally CAH10 : After dissociation of CA.025 0.. were obtained as described in the Setting time measurement section.77 2.5% the setting of CAC occurs immediately after the addition of lithium chloride.59 1.06 0.1% the setting time occurs during the mixing time.24 0. The reason for this is discussed next. 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. This stores the entire set of temperatures once every second.0010 0.90 11.0075 0.12 0. any change of its temperature was kept as slow as possible.0025 0. 252 Note: F denotes setting of the CAC with lithium chloride during the mixing. as the principal mineral in CAC.0050 0.50 ª: mmol/kg 0 0. 1998). The experimental data are simultaneously transferred to a personal computer. formation of a metastable gel and subsequent precipitation (Sorrentino et al.10 0. Comparison of setting time for different quantities of lithium chloride addition The hydration process of CA. Vrbos and Sipusic Motor Thermostat Cooling Pt100 data logger PC TC data logger Pt 100 Vicat needle r h T constant 2R Figure 1. 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. An eight-channel data logger with a 20 bit resolution was used to collect the temperature measurements.00050 0. twisted-shielded wiring.5 3 10À4 %. 1995.00025 0.18 0. In order to have accurate cold junction compensation. whereas with the fraction of 0. The results on the investigated effect of various alkali metal chlorides on the setting time of CAC are presented in Table 4.00075 0. Taylor. 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. As the addition of LiCl increases. leading to the crystalline CAH10 : Solid-state nuclear magnetic resonance .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 ﬁnal setting times.
while differences between the other cations are not great and exhibit a deﬁnitive trend. Of the alkali ions studied.. The inﬂuence of alkali metal chloride addition on the ﬂexural and compressive strength of CAC pastes has been studied.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 ª ¼ 3 mmol/kg tf : s 1371 11 293 12 927 12 660 12 820 Table 4. Li. 1987). The results of measurements are given in Figures 2–4. 1998). Effect of alkali metal chlorides on evolution of ﬂexural strength of CAC pastes 253 . The precipitation of lithium hydrometaaluminate is responsible for the rise of compressive strengths of CAC samples at very early ages (t . because lithium ions show a drastic effect. 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 w 0·05% Figure 3. Comparison of setting times parameters for alkali metal chlorides additions (0. 2007). 1962).Advances in Cement Research Volume 24 Issue 5 Inﬂuence of metal chloride salts on calcium aluminate cement hydration ˇ ˇ ´ Ukrainczyk. but the hydration products of CA. Na . lithium salts cause strength development at early ages.. The ox-obridge condensed structure will be affected by alkali metal cations forming coordination linkage with the hydroxyl groups (Currell et al. The induction period during the precipitation of CAC hydration products from a supersaturated solution is a reﬂection of the nucleation barrier to the formation of these compounds (Barret et al.. promoting the nucleation of the hydration products. 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. while Naþ . 1984). Vrbos and Sipusic w ¼ 0.. K . Rodger and ´ Double.. Rbþ and Csþ will form octahedral symmetry (Wells. caused by an initially fast precipitation of lithium hydrometaaluminate (Matusinovic et al. Liþ behaves differently from the other alkali cations because of its ability to form tetrahedral symmetry with hydroxyl groups.05% mass fraction and 3 mmol/kg) Flexural strength: MPa imaging data indicate that aluminium in CA is entirely fourcoordinated. The accelerating effect of lithium has been attributed to removal of this barrier. which still need further clariﬁcation. which acts as a heterogeneous nucleation substrate. K þ . 1994. This order is in agreement with the decrease of ionic radius of the metals. Rb . CAH10 and C3 AH6 contain six-coordinated aluminium (Taylor. while C2 AH8 also contains four-coordinated aluminium located in the interlayer of this double-layer hydroxide phase (Ukrainczyk et al. The setting time of CAC decreases in the following order: Cs . 1974). 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. This is proved by the present experimental results (Table 4). 10 h) resulting in higher strengths compared 60 50 40 30 20 10 0 0 5 10 t: h 15 20 LiCl w 0·050% w 0·025% w 0·010% CAC Figure 2.
The inﬂuence of alkali metal chlorides on evolution of ﬂexural and compressive strength of CAC pastes is presented in Figures 3 and 4. while Rodger and Double (1984) and Currell et al. Rb . Owing to a high sensitivity of setting time variations with temperature. For the alkali metals we have investigated a correlation according to Equation 1. 1984) or semi-isothermal (Grifﬁths et al. Effect of alkali metal chlorides (w ¼ 0. Li. During the hydration of CAC. 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. Ukrainczyk and Matusinovic.. Rodger and Double. This is similar. 1984). The lithium ion . The setting time of CAC decreases in the following order: Cs . 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. Rb . This transformation is accelerated by temperature and moist conditions. Furthermore. the heat (or temperature) evolution curve is signiﬁcantly different.05%) on evolution of compressive strength of CAC pastes to the reference (plain) CAC sample. while Currell et al. the corresponding long-term strength reduction (Figures 3 and 4) is only somewhat more pronounced in comparison to other alkali cations. 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. ´ 2010). Murat and Sadok (1991) employed mathematical modelling based on a modiﬁcation of the expression of nucleation free enthalpy (relying on a hypothesis of homogeneous nucleation). such poorly controlled temperature conditions could explain the confusing results in the literature. This model (Equation 1) has been previously veriﬁed on experimental results of calcium sulfate hydration (anhydrite and hemihydrate). The strength reduction pattern for lithium has a higher reduction effect. Na .. respectively.05% was taken for further research. respectively. Rodger and Double (1984) indicated that sodium and potassium behave as retarders (25 mmol/kg). which in the dilute solution approximation leads to the following single equation 1: ln (rn ) ¼ a þ b=R where rn is the nucleation rate approximated to (1/t0 ). but not as drastic to the setting behaviour. in Grifﬁths et al. The increase of the strength is caused by precipitation of lithium hydrometaaluminate. 1987. The results are shown in Figure 5. resulting in different tmax values. K . in different boundary conditions. which causes a considerable temperature increase of prepared specimens (Banﬁll. compared to the reference (plain) CAC paste. (1987) performed semi-adiabatic calorimetric measurements at 22 Æ 28C and 18 Æ 38C. To correlate experimental results of the inﬂuence of various cation additions on the CAC (Secar 71) hydration. although the parameter t0 better corresponds to the real initial setting time as obtained by Vicat measurements. while differences between the other cations are not great and exhibit a deﬁnitive trend. Based on the setting time results in Table 3 the mass fraction of alkali metal chloride addition of w ¼ 0. 1991). which correlates with the ionic radius of the metals. R is the ionic radius and a and b are ﬁtting parameters.Advances in Cement Research Volume 24 Issue 5 Inﬂuence of metal chloride salts on calcium aluminate cement hydration ˇ ˇ ´ Ukrainczyk. a large quantity of total heat is liberated in the ﬁrst 24 h of 254 The results of the present study are in agreement with Grifﬁths et al. (1991) who reported that sodium (Na) and potassium (K) act as accelerators (15 mmol/kg). the authors did the comparison analysis of the setting behaviour according to the time of maximal heat generation (or temperature) tmax instead of t0 . ´ Rodger and Double. Moreover... A higher mass fraction of LiCl causes lesser long-term compressive strengths (Figure 2). On the other hand. that is semi-adiabatic (Currell et al. It is worth noting that although the lithium ion exhibits a drastic setting time reduction (Table 3). 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. (1987) reported sodium as an accelerating but potassium as a retarding admixture. Indeed the effect of salt addition may decrease the hydration rate and postpone tmax as a result of the ﬂattening and stretching of the shape of the main hydration peak (as discussed in the Transition metals section). 1994. It has to be noted that Grifﬁths obtained results from conduction calorimetry at carefully controlled conditions of temperature. K . After about 15 h the strength of the specimens with the lithium addition is lower than the reference strength. (1991) and Rodger and Double (1984). 1995. Li (which is in agreement with the order of the ionic radius of the metals). Na . 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. w 0·05% Figure 4. which acts as a heterogeneous nucleation substrate and promotes the nucleation of the calcium aluminate hydrates.. where t0 is the experimentally determined setting time. It can be seen that all alkali metal salts decrease compressive and ﬂexural long-term strengths of CAC. The extent of this reduction in strength follows the same order as for the setting time reduction: Cs .
15 450. 6.5% of salts for calcium (Ca) and strontium (Sr) brought about setting times close to that in the absence of any admixture. potassium (K).50 9.53 315.1% 0. 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.54 24. was obtained as described in the Setting time measurement section. The highest concentration (w ¼ 5%) of calcium (Ca) and strontium (Sr) resulted in a ﬂash set during mixing.0% Figure 5.52 45. It can be observed that lower concentrations (0. respectively. 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. not ﬁxing the molar concentrations.05% the corresponding molar concentrations for lithium (Li).0 mmol/kg. as already detailed above.06 180.0% ª: mmol/kg 2. from Figure 5 it is obvious that constant mass concentration is not an adequate parameter for the analysis.11 63.05 525.7. Addition of 0.5 mmol/kg.03 90. Alkaline earth metals Measurements of the initial and ﬁnal setting time parameters. Calculated molar concentrations in mmol/kg of CAC for a corresponding mass fraction 255 . respectively. Investigation of the correlation according to Equation 1. 4.8. the present experiments on the inﬂuence of alkaline earth metal chlorides were conducted with a constant mass concentration.6. Unfortunately.1% or 400 Setting time: min 300 Mg Ca Sr Ba 200 100 0 0 100 200 300 γ: mmol/kg CAC 400 500 Figure 6.02 210. This signiﬁcant increase of molar concentrations from the reference concentration of 3. Inﬂuence of alkaline earth metal chloride addition on the initial setting time of CAC pastes (horizontal line: value for plain CAC) 3·0 2·5 2·0 1·5 w 0·05% γ 3 mmol/kg Linear fit Li ln(1/ti) 1·0 0·5 0 0·5 1·0 1·5 Cs ln(1/ti) 1·36 R 0·92927 K 24/r Rb Na CAC 0·006 0·008 0·010 1/r: pm 1 0·012 0·014 up to 10.1 and 3.5% 1. For w ¼ 0.0% MgCl2 3 6H2 O CaCl2 SrCl2 3 6H2 O BaCl2 3 2H2 O 10.92927). while magnesium chloride (MgCl2 ) has the weakest acceleration effect. while barium (Ba) and magnesium (Mg) showed signiﬁcant acceleration. focusing on 5.31 4.0 mmol/kg results in further/higher increase of the setting time.08 48. In order to compare the results. Vrbos and Sipusic is omitted from the regression analysis because of its drastically different behaviour. sodium (Na).8 to 525 mmol/kg on the setting time is presented in Figure 6.Advances in Cement Research Volume 24 Issue 5 Inﬂuence of metal chloride salts on calcium aluminate cement hydration ˇ ˇ ´ Ukrainczyk. The results presented here are compared with the available literature results obtained on Lafarge iron-rich CACs.17 96. 8. according to Table 5) resulted in a retardation of the setting behaviour. For a constant molar concentration (3 mmol/kg) the regression analyses resulted in a reasonably good correlation coefﬁcient (R ¼ 0.21 126.12 Table 5.42 240. Furthermore.80 52. as shown in Table 5.05 31. As expected. ti is measure in hours (horizontal line: value for plain CAC) w 0.01 6. The effect of a range of molar concentrations from 4.01 105. A further increase of admixture concentration results in a dramatic acceleration of the setting time in the presence of any of the four salts. a range of the prepared mass concentrations (fractions relative to weight of cement) were transformed to molar concentrations. that is ti and tf . rubidium (Rb) and caesium (Cs) are 11.
it is interesting to compare the present study’s results to the literature results obtained on a completely different class of CAC. tri. resulting in CA and CA2 as the main mineral phases with no C12 A7 .and tetra-valent) have an accelerating effect on the setting of Secar 71. large amounts of AH3 gel are produced (Edmonds and Majumdar. although CaCl2 (with the second highest molar concentration.. as well as sensitivity to different chemical compositions of the similar iron-rich cements investigated. Effect of alkaline earth metal chlorides (w ¼ 1%) on evolution of ﬂexural strength of CAC pastes . Because alkaline earth metal cations bear the same charge they behave in a chemically similar way. It is known that the presence of small quantities of C12 A7 (in iron-rich CAC) or CA2 (in Secar 71) inﬂuence the duration of the induction period: C12 A7 accelerates the nucleation. Rodger and Double.71. acceleration or retardation) with the molar concentration. Moreover. With an increasing C/A ratio the length of the induction period diminishes. Later. Upon hydration of CA2 .. 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. 1989) as a ﬁrst hydration product.e. thus modifying C/A ratio in the solution. In agreement with the ﬁnding of the present study. On the other hand.. The differences in the literature regarding the effect of alkaline earth metal chlorides could be attributed to the change of the set behaviour inﬂuence (i. and signiﬁcant retardation at higher concentrations (from 50 mmol/kg to 250 mmol/kg). temperature of hydration and method of obtaining the setting parameters. when the lime concentration reaches a sufﬁcient level. 1987. 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. 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 ¼ 163. The results of measurements are presented in Figures 7 and 8. the chemical composition of cement inﬂuences the change of the C/A ratio in the liquid phase. care should be taken in this interpretation because they differ substantially in their properties. 1973) thereby inevitably initiating the precipitation of AH3 gel. The present study’s results also conﬁrm the different behaviours of strontium (Sr) and barium (Ba) ions as reported by Rodger and Double (1984). Refractory Secar 71 CAC. Moreover. This has been 256 shown by hydrating a series of synthesised CA samples prepared with C/A ratios ranging from 0. that has a high aluminium oxide (Al2 O3 ) content of about 70%). produced by Lafarge. This difference may be principally explained by the C/A ratio of the liquid phase during the nucleation period. Nikushchenko et al. 1984). bi-. that is contrary to the present ﬁndings. which also differs from most other studies on iron-rich CACs as summarised in the introduction. Grifﬁths et al. a pure CAC Secar 71 (produced by Lafarge.0 min) but higher strength reduction than calcium chloride (CaCl2 ). The mass concentration of w ¼ 1% was chosen to investigate the inﬂuence of alkaline earth metal salt additions on the ﬂexural and compressive strength of CAC pastes. principally chemical and mineralogical composition. C4 AF and C2 S. Although the inﬂuence of additions on setting behaviour of these two different classes of CAC has been compared in the literature.96 to 1. The results of the current study have shown that the inﬂuence of alkaline earth metal chlorides additions on setting behaviour of iron-rich CAC and refractory Secar 71 CAC is completely different.5 min) the compressive and ﬂexural strengths exhibit the lowest reduction from the reference ones (with no admixtures). They showed that alkaline earth metal additions in low concentrations (12. The dissolution of the ‘pure’ C12 A7 exhibits a C/A ratio of exactly 1. 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). 1991. compared to the reference (plain) CAC paste. Moreover.5 mmol/kg and 25 mmol/kg) exhibit acceleration of the setting. resting on the hypothesis of the same hydration mechanism of CA mineral. This suggests that the hydration mechanism of the two CACs may be quite different. has an aluminium oxide (Al2 O3 ) content of about 70%. Interestingly. Nilforoushan and Sharp (1995) reported an inverted (opposite) trend of the results in Figure 6. Thus. thus the addition of alkaline earth metal salt increases ‘apparent calcium’ concentration. showing unambiguously the congruency of its dissolution. Table 5) results in the strongest acceleration of the initial setting time (t0 ¼ 69. strontium chloride (SrCl2 ) and barium chloride (BaCl2 ) (with the smallest molar concentrations) show no signiﬁcant acceleration effect (Figures 7 and 8) 12·5 12·0 11·5 11·0 10·5 10·0 9·5 9·0 8·5 8·0 7·5 7·0 6·5 6·0 5·5 0 5 10 15 t: days Flexural strength: MPa CAC Mg Ca Sr Ba 20 w 1% 25 30 Figure 7.Advances in Cement Research Volume 24 Issue 5 Inﬂuence of metal chloride salts on calcium aluminate cement hydration ˇ ˇ ´ Ukrainczyk. C2 AH8 precipitates coinciding with an acceleration of the hydration reaction rate. with an opposite effect of salts concentration on setting behaviour.. calcium (Ca) is reported by all three groups of researchers (Currell et al.04 (Galtier and Guilhot. Murat and Sadok (1991) reported that all chloride metal salts (mono-.05–1.10 (Fujii et al. The dissolution of the ‘pure’ main mineral CA shows the C/A ratio to be in the range 1. 1986. whereas CA2 retards it. 1984) to act as a retarder. Alkaline earth metal salts decrease compressive and ﬂexural long-term strengths of CAC.
1986): one ﬁtted through the induction period of the curve and the other ﬁtted through the inﬂection point of the rising slope of the main peak. ª ¼ 10 mmol/kg of CAC 257 . Initial set is acquired from the intersection of two straight lines (Bushnell-Watson and Sharp. Setting can be attributed to the interlocking of the hydration products when their formation takes place to an appreciable extent. the time of ﬁnal set tf was found to be 9 min Æ 1. It was found that the difference between the initial setting time obtained by the two methods. on the hydration of the pure phases with foreign cation additions).5 min below the point of inﬂection (Figure 9).2 min Æ 0. which can replace the calcium in the hydration products and/or even form novel hydration products that change the rate of hydration development and inﬂuence strength development. Further research is needed to investigate the nature of the hydration products formed (e.6 min. In a more ﬂuid paste. Vrbos and Sipusic 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. In this paper times of initial. 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. An example of a temperature evolution of a specimen during simultaneous standard Vicat method measurement is shown in Figure 9. After moulding the cement paste and ﬁxing of the thermocouple within a few minutes. The experiment on plain cement paste (without admixtures) was repeated ﬁve times. as illustrated in Figure 9. Effect of alkaline earth metal chlorides (w ¼ 1 %) on evolution of compressive strength of CAC pastes Figure 9. These results indicate the role of the foreign cations. sets for experimental series on transition metals were established from the obtained time–temperature curves. 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. Interestingly. and ﬁnal. The inﬂuence of the sample mass and heat transfer boundary conditions can be analysed by comparing Figures 9 and 10 (for the plain CAC). are isothermal calorimetry.g. (ti À t0 ) was only 1. Temperature evolution of specimen during standard Vicat method measurement but exhibit the highest strength reduction (Figures 7 and 8). the Vicat initial setting time is signiﬁcantly affected by the water-tocement ratio attributable to the consistency of the paste being tested. Unlike calorimetry or temperature rise measurements. This reﬂects the fact that the setting time is an arbitrarily deﬁned parameter. Effect of transition metal chlorides on the temperature evolution of CAC. In order to conduct the comparison of the values of setting time parameters obtained by Vicat method and temperature rise measurements. although less traditional and indirect. The ﬁnal set was approximated as the point of maximal heat generation. temperature rise and solution conductivity measurements. the temperature of the specimen in a Vicat mould was measured as described in the CAC temperature evolution measurement set-up section. chemical dissolution CAC 23 Co Mn Cu γ(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. a decrease of temperature is occurring owing to the dissipation of the heat generated by the initial wetting of cement.Advances in Cement Research Volume 24 Issue 5 Inﬂuence of metal chloride salts on calcium aluminate cement hydration ˇ ˇ ´ Ukrainczyk. tf . t0 . This validates the further use of the employed alternative method to obtain accurate values of the setting time parameters.
is reached signiﬁcantly later after the onset of the acceleration period in Figure 9 than in Figure 10. Conduction (semi-isothermal) calorimeters have small temperature rise of the samples.. so the hydration rate decreases because of the free water consumption and reaches zero value upon water insufﬁciency. Grifﬁths et al. whereas semi-adiabatic calorimeters have small heat transfer to the surroundings. Rodger and Double. enthalpy change accompanying solvation of cations by water molecules or melting point of pure metals. Rodger and Double (1984) are the only researchers who investigated the effect of transition metal chlorides on iron-rich CAC (manufactured by Lafarge). the heat (or temperature) evolution curve is signiﬁcantly different. 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. plotted against the added cation’s atomic number pKa . For an isoperibol calorimeter. 2010).. probably the result of following the Vicat standard procedure. One point is the poor control of the starting temperature (e. Currell et al. As the rate of transformation reactions of metastable products to the stable C3 AH6 and AH3 is signiﬁcantly increasing with the temperature.. Variation of time of maximum temperature rise of CAC samples (see text for details) and acidity of crystalline Me(OH)2 quantiﬁed by pKa value. 2010)). In different boundary conditions. Istra cement. A second point is that.208C shows the high inﬂuence 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. Ukrainczyk and Matusinovic. Interestingly. 1984). In order to clarify this ﬁnding. 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.g. 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. For example. A well-deﬁned trend can be observed in the inﬂuence of transition metals on setting behaviour. 258 Transition metals To the best of the current authors’ knowledge. the regularity of the setting times observed in Figure 11 follows the same principle. It is well known that various trends are observed when studying chemical reactions or some physical properties within the transition metal group. tmax . The present authors analysed the results of Rodger and Double against the added metallic atomic number. as depicted in Figure 11.. 2002. 1987. They reported the time of maximum temperature rise of CAC samples (w/c ¼ 0.Advances in Cement Research Volume 24 Issue 5 Inﬂuence of metal chloride salts on calcium aluminate cement hydration ˇ ˇ ´ Ukrainczyk. the temperature ´ evolution of the material strongly depends on the heat transfer boundary conditions around the testing specimen. Z 29 Co 2 2 2 6 t(Tmax): min 4 Ni2 CAC 3 2 30 Figure 11.. Ukrainczyk and Matusinovic. 1991. 2001). Fryda et al. The ‘shoulder’ in Figure 9 before reaching tmax is a consequence of the signiﬁcant commencement of the transformation reactions (Fryda et al. (1987) or Rodger and Double (1984) or semi-isothermal as in work by Grifﬁths et al. The cement hydration ´ is incomplete if there is not enough water for stoichiometric hydration. Ukrainczyk and Matusinovic. previously not addressed in the literature. The hydration of CAC at temperatures ´ below . Some authors (Currell et al. 2010). 2001. 1995. that is semi-adiabatic as in work by Currell et al..5 with 25 mmol of salt per kg of CAC) in semi-adiabatic conditions. on the hydration of similar (same class) CAC from a different manufacturer (namely. Vrbos and Sipusic and partial hydration before reaching the induction period with very small heat generation (Banﬁll. Ukrainczyk and Matusinovic. 2001. The cause of such behaviour is qualitatively explained by the gradual ﬁlling of the 3d-orbital by electrons taking into account Hund’s rule of maximum multiplicity. and so on. 1987. The acidity of the precipitate can be described by the following chemical reaction in base media 2: MeðOHÞ2 ðcr:Þ þ OH À ðaq:Þ $ MeðOHÞ3 À ðaq:Þ pKa curve t(Tmax) curve 1000 Zn2 5 Cu 800 Mn 600 Fe2 400 25 26 27 28 Atomic number. 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). owing to a rapid hydration of CAC with a corresponding high heat generation effect (about 20 mW/g in isothermal conditions (Banﬁll. part of this paper is devoted to investigating further the inﬂuence of transition metals. which could result in signiﬁcantly different tmax values. 2010). Fryda et al. (1991) or Murat and Sadok (1991). 1995. in the form of chloride salts. 2002. This also explains why the time of ´ maximal temperature rise. the associated free water liberation allows further reaction of cement and thus increases the hydration rate (Bensted. Calucem). In non-isothermal conditions (Figure 9) the temperature increase is higher due to lower heat loss to the environment. Rodger and Double. which is written for measurements on a PC that does not have such pronounced temperature sensitivity as CAC.
3 mW/g (Banﬁll. 1995. With the addition of the transition metal chlorides the main hydration peak of the temperature evolution curve becomes ﬂatter and longer (with a lower value of maximal temperature at tmax ) in the following order: Co . ti is measured in hours 259 . These values for pKa correspond to the fully crystalline hydroxide precipitate. 1991). are obtained from thermodynamic data (Shkol’nikov.25 as opposed to 0. 1989). w/c ¼ 0. the discrepancies in quantitative agreement can be ascribed to the complexity of the real chemistry behind the studied process of CAC hydration. The retardation effect is higher for 200 25 26 27 28 Atomic number. The results are plotted against the reciprocal values of ionic radii (Shannon. The inﬂuence of transition metal chloride addition (ª ¼ 10 mmol/kg) on the setting time of CAC pastes is depicted in Figure 12. Results of temperature evolution measurements for pastes prepared with ª(Me2þ ) ¼ 10 mmol/kg are shown in Figure 10. Vrbos and Sipusic Setting time: min The values of acidity constants. The induction period is followed by the onset of the accelerated stage of reaction due to massive precipitation of hydrates. Cu . The concentration of 100 mmol/kg showed no setting behaviour within 30 h of hydration. which relies on an assumption of homogeneous nucleation (Murat and Sadok. 1976) in order to test the validity of Equation 1. the setting time of the CAC is more prolonged. This concept of acid/base reactions and the inﬂuence on the setting time of calcium aluminate cement is also corroborated by Mohmel and Gessner (1997). Ukrainczyk and Matusinovic. Comparison of results obtained in the present study with those presented in the literature. Mn . Z 29 30 Figure 12. The maximal temperature rise is reached in only a few hours after the onset of the accelerated stage. the experimental data from the present study reproduced the deﬁned trend of the change of setting times against the added cation’s atomic number well. the suggested explanation is that the more the acid/base properties (real pKa values) of transition metal precipitates deviate from the aluminum hydroxide. It is clear that the 1·2 1·4 1·6 1·8 Co Ni Fe ln(1/t0) 2·0 2·2 2·4 2·6 2·8 3·0 Zn Mn Cu Current paper Rodger and Double (1984) 0·0135 0·0140 0·0145 0·0150 0·0155 0·0160 0·0165 1/r: pm 1 Figure 13. Zn. which is in accord with results obtained by Rodger and Double (1984). 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. The results of Rodger and Double have lower (more negative) values of ordinate.e. 100 mmol/kg and 10 mmol/kg. 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. ti 600 tmax 500 Cu2 400 Mn2 Co2 Zn2 AlðOHÞ3 ðcr:Þ þ OH À $ AlðOHÞ4 À ðaq:Þ 300 The reaction in Equation 3 has pKa ¼ 5. The effect of various transition metal chlorides on the setting time of CAC is investigated for two concentrations. Calcium hydroxide has no observable acidic properties.50). which corresponds to the longer absolute setting time values (compare Figures 10 and 11). Inﬂuence of transition metal chloride addition (ª ¼ 10 mmol/kg) on the setting time of CAC pastes (horizontal lines: values for plain CAC) higher concentrations. No signiﬁcant temperature rise is observed during the induction period owing to a small and constant rate of heat generation (about 0. 2005) and plotted in Figure 11. ´ 2010)). Generally. pKa .Advances in Cement Research Volume 24 Issue 5 Inﬂuence of metal chloride salts on calcium aluminate cement hydration ˇ ˇ ´ Ukrainczyk. who showed that acid/base properties of corundum ﬁller signiﬁcantly inﬂuence the setting of CAC.9 (Nordstrom and May. In agreement with the ﬁnding in Figure 11. 1984) is depicted in Figure 13. Overall. 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 obvious that all investigated transition metal chlorides act as retarders. Aluminium also participates in this type of acid/base equilibrium according to the following reaction 3: 700 Initial setting time. This ﬂattening and stretching effect of the main hydration peak supports the notion of slower growth and crystallisation of hydration products. The results are plotted against the atomic number. primarily owing to the much lower water-to-cement mass ratio employed in this investigation (i. The inﬂuence 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). A comparison of the obtained results with the literature (Rodger and Double.
Mn . Effect of transition metal chlorides (ª ¼ 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. Murat and Sadok (1991) reported that transition metal chlorides have an accelerating effect. 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. Vrbos and Sipusic experimental data signiﬁcantly deviate from the model in Equation 1. gel coatings that hinder crystallisation and growth of the hydration products. Thus. 7 and 28 days are presented in Figures 14 and 15. which has the setting time the closest to the plain 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. Effect of transition metal chlorides (ª ¼ 10 mmol/kg) on evolution of ﬂexural strength of CAC pastes (horizontal lines: values for plain CAC). Z 29 Cu2 Mn2 Conclusions Addition of alkali metal salts accelerates the setting time of CAC in the following order: Cs . A reasonable correlation was observed between setting time and the ionic radius of alkali metals. Rb . 260 . Li. The effect of ﬂattening and stretching of the main hydration peaks observed in Figure 10 could thus be explained by a formation of larger quantities of. promoting the nucleation of the CAC hydration products. Generally. 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. small quantities of lithium salts cause Zn2 30 Figure 14. The inﬂuence of transition metal salt additions on the ﬂexural and compressive strength of CAC pastes was studied. On the contrary.Advances in Cement Research Volume 24 Issue 5 Inﬂuence of metal chloride salts on calcium aluminate cement hydration ˇ ˇ ´ Ukrainczyk. Flexural strength: MPa 12 11 10 9 8 7 6 5 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. The results of measurements of ﬂexural and compressive strength at 1.. 14 13 CAC Co2 28 days 7 days 1 day Figure 15. lithium hydrometaaluminate) that act as a heterogeneous nucleation substrate. the addition of transition metal salts decreases compressive and ﬂexural strengths of CAC. Horizontal lines represent experimental values of strength for the plain CAC. This order is in agreement with the magnitude of the strength reduction in Figures 14 and 15. Zn. the cobalt (Co) sample. Co . compared to the reference (plain) CAC paste. achieves the smallest reduction in strength. as discussed in the Earth alkali metals section. 1997). and/or more impermeable. Cu . K .g. which are increasing with age. This order is in agreement with the increase of ionic radius of the metals. through an initially fast precipitation of alkali metal hydration products (e. which block hydrolysis and inhibit growth of the crystalline hydration products. The accelerating effect of alkali metals has been attributed to the removal of the nucleation barrier. the nuclei formed being grains of metallic hydroxide (or hydrated aluminates for Liþ and Ni2þ ions in the form of double-layer hydroxide phases) that lead to an increase of the nucleation rate. Again. Compressive strength: MPa 85 80 75 70 65 60 55 50 45 25 26 27 28 Atomic number. Along with rapid setting. the strength reduction may be primarily attributed to the lower hydration degree achieved owing to the retardation of the hydration reaction rate (Figure 10). excluding lithium (Li). In the present case of iron-rich CAC. the zinc (Zn) addition results in the highest retardation of the setting time and exhibits the highest reduction in strength. Na . It was observed that the relative degree of hydration after 24 h has a tendency to lower in the following order: none . For example. This suggests that the hydration mechanisms of these two classes of CAC are signiﬁcantly different (as discussed in the Earth alkali metals section). the inﬂuence of transition metal chloride additions on setting behaviour of iron-rich CAC and refractory Secar 71 CAC is shown to be completely different. respectively. Murat and Sadok (1991) have explained the acceleration effect by an hypothesis of a heterogeneous nucleation process.
Bushnell-Watson SM and Sharp JH (1986) The effect of temperature on the setting behaviour of refractory calcium aluminate cement. Midgley HG and Parsonage JR (1987) The acceleration and retardation of set high alumina cement by additives. so they can be used for preparation of rapid hardening cement-based materials – for example. and the setting is retarded in the following order: Co . Journal of the American Ceramic Society 69(4): 361–364. The extent of strength reduction followed the same order as for the setting time reduction. Setting times were established from the time–temperature curves obtained. Cement and Concrete Research 16(6): 875–884.1%) resulted in a retardation of the setting behaviour. Jantzen C. Vrbos and Sipusic strength development of CAC at early ages. The results of the setting time obtained from the measured temperature evolution of cement pastes were compared to the standard Vicat needle measurements. even when mixtures are prepared with different water-to-cement ratios. sulphate and seawater solutions. A further increase of admixture concentration results in a dramatic acceleration of the setting time. Calcium Aluminate Cements (Mangabhai RJ (ed. Magnitude of strength reduction for all tested ages follows the order observed for the setting time retardation. Johnson A. Cu .)). The difference between the initial setting time obtained by the two methods is only 1. Edmonds RN and Majumdar AJ (1989) The hydration of Secar 71 aluminous cement at different temperatures. UK. pp. George CM (1983) Industrial aluminous cements. 227–246. In Proceedings of International Conference on CAC. Part 2: Effect of temperature on the hydration reaction.2 min Æ 0. The retardation effect may be explained by the precipitation of protective gel (amorphous) coatings on the phase boundary surface of cement grains. This will enable a better comparison of the results among researchers.)). REFERENCES Banﬁll PFG (1995) Superplasticizers for Ciment Fondu. Low concentrations (0.Advances in Cement Research Volume 24 Issue 5 Inﬂuence of metal chloride salts on calcium aluminate cement hydration ˇ ˇ ´ Ukrainczyk. 114–138. Mn . Journal of the American Ceramic Society 76(2): 409–416. London. With the addition of the transition metal chlorides the main hydration peak of the temperature evolution curve becomes ﬂatter and longer. Fryda H. pp. Grzeskowlak R. Cong X and Kirkpatrick RJ (1993) Hydration of calcium aluminate cements: a solid-state 27 Al NMR study. IOM Communications. UK. 125-12529702983 ‘Development of hydration process model’. pp. Read D and Stegemann JA (2010) 261 . Galtier P and Guilhot B (1984) Conductimetrie. 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A well-deﬁned trend. hydration. London. Cement Concrete Research 19(2): 289–294. Al-Qaser ANF and Mangabhai RJ (1991) Calorimetric studies on high alumina cement in the presence of chloride. The strength reduction may be primarily attributed to the lower hydration degree achieved due to the retardation of the hydration reaction rate. in Structure and Performance of Cements. Spon Press. London. London. A simple method of analysing CAC hydration based on the measurement of temperature rise of cement pastes was described. Applied Science. The inﬂuence 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. pp. 415–470. Cement and Concrete Research 4(4): 545–556. while the compressive and ﬂexural strengths exhibit the lowest reduction from the reference material. 2nd edn (Bensted J and Barnes P (eds)). Cement and Concrete Research 14(5): 679–685. Acknowledgement The authors acknowledge support from the Croatian Ministry of Science. UK. In Calcium Aluminate Cements 2001 (Mangabhai RJ and Glasser FP (eds)). 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. Alkali metal salts deteriorate/ reduce compressive and ﬂexural long-term strengths of CAC. Calcium addition results in the strongest acceleration of the initial setting time. Advances in Cement Research 7(28): 151–157. This suggests that the hydration mechanisms of these two classes of CAC are signiﬁcantly different. Grifﬁths DL. Chapman and Hall. Scrivener KL and Chanvillard G (2001) Relevance of laboratory tests to ﬁeld applications of calcium aluminate cement concretes. Currell BR. The retardation effect is higher for higher concentrations. Education and Sports under projects no. 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