Fly ash cements: correlating cement additives performance with chemical composition of fly ashes Paolo Forni 1 *, Matteo Magistri 2 1. R&D Cement Additives Division, Mapei SpA, Milan, Italy 2. R&D Cement Additives Division, Mapei SpA, Milan, Italy Abstract Supplementary cementitious materials keep increasing their importance worldwide. Fly ash, blastfurnace slag, limestone, natural pozzolanas can substitute clinker in cement composition, improving sustainability and economics of cement manufacturing. However, their use can lead to a loss of performances (namely strengths) that limits the maximum amount of clinker substitution. The present study would like to be the start of a thorough practical understanding of the effect of high substitution by fly ash. Effects on strength have been studied for several fly ash and clinker combinations, correlating performance to chemical composition. In addition, treatment of fly ash cements with chemical additives (grinding aids/quality improvers to be added during cement manufacturing) has been studied. This allows the recovery of the decreased performances, opening the door for higher substitutions of clinker without losing strength. In conclusion, the results can provide insight on specific fly ash selection by a cement manufacturer, in combination with chemical enhancers of the hydration. Originality To the authors knowledge, no previous studies of this type exist of the correlation between chemical and mineralogical composition of fly ashes, in combination with chemical additives, and the properties of finished blended cement. Keywords: Cement; fly ash; clinker; SCM; chemical additives 1 Corresponding author: p.forni@mapei.it, Tel +39-2-37673757, Fax +39-2-37673214
1. Introduction As it is well known and reported in many occasions, one of the most effective ways to lower the manufacturing cost of cement is by lowering the clinker factor. Clinker is the single most expensive component of cement, due to the high-energy process required to obtain it in the kiln. Many standards all over the world allow for the manufacturing of blended cements, where part of the clinker is substituted by supplementary materials as limestone, fly ash, or blastfurnace slag. These secondary materials are directly ground together with clinker and gypsum, or milled in a separate stage, followed by blending with ordinary Portland cement. Each of them provides advantages and disadvantages (related to cost, grindability, chemical reactivity, availability) that can drive their specific application. Fly ash is one of the most widely available supplementary cementitious materials, being the byproduct of coal burning in power plants. During the burning, fused fine particles are carried away by the flue gas and solidify by cooling to glassy amorphous ash particles with a glass content of approximately 6-85% in weight (Lutze and vom Berg, 4). Composition in terms of crystalline phases and chemical elements has been investigated by many authors (e.g. in Prause, 1991, Richartz, 1984 and Kautz and Prause, 1986). Hydration reaction in alkaline conditions is the phenomenon that allows their extensive use as a clinker replacement: overly simplifying, this consists in the reaction of amorphous silica contained in the ashes with the calcium hydroxide produced by the hydration of cement clinker. This means that the effectiveness of the ashes in providing strength through the formation of C-S-H gel is mainly focused at later ages, since some time is needed to thoroughly spread the presence of Ca(OH) 2 in the matrix of cement to get it reacting with the fly ash particles. Hence, blended cements based on the substitution of clinker with fly ashes usually suffer from lower early strengths (Fraay, 199, Huettl,, Lee C. Y. et al., 3, Mueller et al.). Several studies have been published regarding the activation of fly ash through chemical compounds, both inorganic (e.g. alkali sulphates) and organic (e.g. alkanolamines) (Gartner and Myers, 1993, Sandberg, 8, Scholze, 1977). In particular, triethanolamine (TEA) has been the subject of several investigations regarding the activation of blended cements containing fly ashes or other secondary components (e.g. in Lee C. Y. et al., 3). Additional work has been done to try and correlate the chemical composition of fly ashes with their reactivity (Schulze and Rickert, 11). This study was carried out by preparing artificial cement pore solutions and varying different parameters. 1.1 Purpose of the work In the present work, we try to take a move towards the field application, by trying to investigate the possible correlations between the fly ash composition and its reactivity in blended cements, with and without the presence of chemical activators normally used in the cement industry. The chosen approach is on purpose very practical: two industrial clinkers were selected, together with four different fly ashes, analysed for their composition, ground and mixed to yield blended cements with % fly ash content. These cements were used to prepare EN-196/1 mortars and determine compressive strengths. Strengths were measured on blank cements and by adding chemicals in the mixing water. The strengths results were then analysed to assess any correlation. Data obtained through this work are not conclusive: additional investigation should and will be carried out to confirm the findings and better understand the mechanism of hydration of fly
ashes in their practical application as a clinker substitute. 2.Experimental 2.1 Cements and fly ashes The following materials were selected for the investigation: two Portland cement clinkers (coded C4564 and C475) one natural gypsum (dihydrate) four fly ashes (coded C4672, C4736, C4737 and C4738). Criteria followed in choosing were to avoid very particular material, trying to focus on typical characteristics that could have the widest interest. The two clinkers come from different geographical areas, the fly ashes were the byproduct of different coals burned in different power plants. Each clinker and gypsum were ground together in a laboratory mill for a standard time, in the ratio 95:5. Enough of these Ordinary Portland Cements (OPCs) was ground for all the tests, and thoroughly mixed and homogeneized to avoid any effect of fineness variation between grinding batches. Fly ashes were used as they were received: all of them were provided ready to use, i.e. dry and already at a fineness compatible with direct use in cement. Blended fly ash cements were prepared by dry blending the OPCs with each of the ashes in the ratio of 8:, yielding 8 different cements (4 for each clinker). For each of these 8 cements, compressive strengths were measured according to EN-196/1, so with standard water/cement ratio of.5 and standard sand/cement ratio of 3:1. For the determination of strengths in the presence of chemicals, the latter were added directly in the mixing water by weighing the appropriate amount of each. For the assessment of chemical and mineralogical composition of OPCs and fly ashes, X-Ray fluorescence (Bruker AXS S8 Tiger), thermogravimetric analysis (TGA Netzsch TG9F1 Iris) and quantitative X-Ray diffraction with Rietveld method were used. Powder diffraction data were collected with a PANalytical X pertpro MPD diffractometer with theta theta geometry, equipped with an X Celerator detector working with the CuKα radiation (1.54184 Å) in the 2theta range 5 8, a step size of.17 2 theta and a scan step time (s) of 12,1. All data collections were performed at room temperature with back-loading sample holders to avoid preferred orientation of crystallites. Data were analysed by the Rietveld method (Rietveld, 1969) using the Bruker AXS software package TOPAS 4.2 operated in the fundamental parameters mode (Cheary et al, 1992, Coelho,, BRUKER AXS, 3). 2.2 Chemical additions As for chemical additions, on each cement and fly ash combinations the following were added (dosages refer to total cementitious): - triethanolamine (TEA) at a dosage of 25 ppm - triethanolamine (TEA) at a dosage of 25 ppm and sodium chloride at a dosage of 5 ppm - triethanolamine (TEA) at a dosage of 25 ppm and sodium thiocyanate at a dosage of 1 ppm Choice of dosages was dictated by actual use of these chemicals in practical use. These chemicals are well known in the practice of chemical strength activators for cement, and several studies are available on their effects (for example in Dodson, 199 and references therein). However, no agreement exists on the actual mechanism of action, apart from the
common acceptance that it is a catalytic type of mechanism, due to the very low amounts of chemicals required and their absent/minimal consumption. At this stage, it is not the purpose of this study to inquire further about these mechanisms. 3.Results Results of clinker XRD-Rietveld and calculated OPC composition are reported in table 1. All values are expressed in %. Composition of fly ashes (XRF data) are reported in table 2. All values are expressed in %. Table 3a and 3b report all the strengths data at 1, 2 and 28 days. In addition to the absolute values in MPa, % increases over the blank are reported. Table 1 - Composition of OPCs (XRD, TGA), % Sample OPC C4564 OPC C475 C 3 S M3 3.5 34.6 C 3 S M1 29. 28.2 C 2 S.2 17.2 C 3 A, cubic 4.4 4.3 C 3 A, orthorombic 1.5 - C 4 AF 6.4 6.9 CaO.5 1. MgO 2.1 1.1 Gypsum (dihydrate) 2.2 2.3 Bassanite -.5 Anhydrite.2 - Calcite -.9 Portlandite 1. 1.2 Arcanite 1.1.8 Ca-Langbeinite -.9 Aphtitalite.6 - Table 2 Composition of fly ashes (XRF), % Sample Fly ash C4672 Fly ash C4736 Fly ash C4737 Fly ash C4738 MgO 1.6 1.54 1.18 1.61 K 2 O.62 1.76 1.74 1.45 Al 2 O 3 29.61 24.29 19.32 27.72 SiO 2 51.43 57.51 6.6 5.74 CaO 5.49 3.36 1.73 5.32 Na 2 O. 1.33.6.44 SO 3.27...28 TiO 2 1.64 1.35.84 1.75 P 2 O 5 1.22.31.23.62 Fe 2 O 3 3.34 6.3 8.71 3.93 Table 3a Clinker C4564 Compressive strengths (EN-196/1), MPa Sample 1d str % 2d str % 28 str % FA C4672 blank 12.7 24. 52.4 FA C4672 TEA 13.7 7.9 23.9 -.4 51.6-1.5
FA C4672 TEA NaCl 14.7 15.7 25.4 5.8 49.6-5.3 FA C4672 TEA NaSCN 16. 26. 26.5 1.4 51.6-1.5 FA C4736 blank 13.1 23. 53.3 FA C4736 TEA 12.8-2.3 23.8 3.5 53.7.8 FA C4736 TEA NaCl 15. 14.5 24.8 7.8 51.4-3.6 FA C4736 TEA NaSCN 15.9 21.4 25.1 9.1 5.8-4.7 FA C4737 blank 11.9 22.2 47.9 FA C4737 TEA 12.8 7.6 22.9 3.2 48.2.6 FA C4737 TEA NaCl 14.2 19.3 23.8 7.2 49.7 3.8 FA C4737 TEA NaSCN 14.5 21.8 24.3 9.5 48.7 1.7 FA C4738 blank 1.6 23.6 53.6 FA C4738 TEA 13.4 26.4 25.3 7.2 56.8 6. FA C4738 TEA NaCl 15. 41.5 26.4 11.9 54.4 1.5 FA C4738 TEA NaSCN 15.3 44.3 26.2 11. 53.3 -.6 Table 3b Clinker C475 Compressive strengths (EN-196/1), MPa Sample 1d str % 2d str % 28 str % FA C4672 blank 13.4 23.2 49.5 FA C4672 TEA 13.6 1.5 24.3 4.7 49.2 -.6 FA C4672 TEA NaCl 15.1 12.7 24. 3.4 48.7-1.6 FA C4672 TEA NaSCN 16.2.9 24.8 6.9 5.6 2.2 FA C4736 blank 13.4 22.2 45.9 FA C4736 TEA 14.3 6.7 23.4 5.4 45.2-1.5 FA C4736 TEA NaCl 14.4 7.5 23.6 6.3 48.9 6.5 FA C4736 TEA NaSCN 15.4 14.9 23.8 7.2 48. 4.6 FA C4737 blank 12.8 22.6 46. FA C4737 TEA 13.7 7. 22.9 1.3 48. 4.3 FA C4737 TEA NaCl 14.4 12.5 22.8.9 46.8 1.7 FA C4737 TEA NaSCN 15.1 18. 24.5 8.4 47.1 2.4 FA C4738 blank 13.9 22.7 5.6 FA C4738 TEA 14.6 5. 23.7 4.4 5.6. FA C4738 TEA NaCl 15.4 1.8 24.2 6.6 49.8-1.6 FA C4738 TEA NaSCN 15.8 13.7 25.1 1.6 49.8-1.6 4.Results discussion and analysis The data analysis that follows focuses on the assessment of any correlation between compressive strength values and chemical composition of the fly ashes. Only the main fly ash components, namely alumina, silica and iron oxide, were considered at this stage. In addition, usual calculated parameters like Silica Ratio (SR) and Alumina Ratio (AR) were considered. Formulas used are the following: Silica Ratio: SiO 2 / (Al 2 O 3 +Fe 2 O 3 ) Alumina Ratio: Al 2 O 3 /Fe 2 O 3 SR and AR for this study were calculated only based on fly ash composition (i.e., not considering contribution of the OPC). 4.1 Clinker C4564
Strengths were plotted versus the chemical parameters and linear correlation equations were calculated. Graphs for each age and chemical parameter (along with the corresponding equations) are shown in Figures 1 to 4. 4 3 1 C4654 - blank - 1d - Al y = -,5724x + 33,242 R² =,17 5 1 15 4 3 1 C4654 - blank - 2d - Al y = 6,169x - 116,6 R² =,9929 22 4 3 1 C4654 - blank - 28d - Al y = 1,3991x - 46,146 R² =,5861 46 48 5 52 54 65 6 55 C4654 - blank - 1d - Si y =,9149x + 46,355 R² =,467 5 5 1 15 8 6 C4654 - blank - 2d - Si 4 y = -5,898x + 192,19 R² =,955 22 66 64 62 6 58 56 54 52 C4654 - blank - 28d - Si y = -1,4748x + 133,8 R² =,71 46 48 5 52 54 1 C4654 - blank - 1d - Fe y =,49x + 3,2587 R² = 8 5 1 15 1 C4654 - blank - 2d - Fe y = -3,33x + 8,48 R² =,9851 22 1 C4654 - blank - 28d - Fe y = -,7981x + 47,77 R² =,7 46 48 5 52 54 2,5 1,5 1,,5 C4654 - blank - 1d - SR y =,483x + 1,2219 R² =,36 5 1 15 2,5 1,5 1,,5 C4654 - blank - 2d - SR y = -,3542x + 1,22 R² =,9765 22 2,5 1,5 1,,5 C4654 - blank - 28d - SR y = -,838x + 6,1462 R² =,6256 46 48 5 52 54 1 C4654 - blank - 1d - AR y = -,38x + 9,2585 R² =,13 5 1 15 1 C4654 - blank - 2d - AR y = 3,7413x - 81,258 R² =,9673 22 1 C4654 - blank - 28d - AR y =,738x - 32,319 R² =,4225 46 48 5 52 54 Figure 1 Correlation between strength (MPa) and chemical composition of fly ashes (%) Clinker C4654, blank
4 3 1 C4654 - TEA - 1d - Al y = 9,8963x - 14,5 R² =,8458 12,6 12,8 13 13,2 13,4 13,6 13,8 4 3 1 C4654 - TEA - 2d - Al y = 3,5389x - 58,516 R² =,5248 22 23 24 25 26 4 3 1 C4654 - TEA - 28d - Al y =,838x - 17,729 R² =,3915 46 48 5 52 54 56 58 8 6 4 C4654 - TEA - 1d - Si y = -8,9296x + 175,5 R² =,7413 12,6 12,8 13 13,2 13,4 13,6 13,8 8 6 C4654 - TEA - 2d - Si 4 y = -3,8839x + 15,52 R² =,684 22 23 24 25 26 66 64 62 6 58 56 54 52 C4654 - TEA - 28d - Si y = -,9642x + 18,1 R² =,5579 46 48 5 52 54 56 58 1 C4654 - TEA - 1d - Fe y = -4,865x + 69,77 R² =,7488 12,6 12,8 13 13,2 13,4 13,6 13,8 1 C4654 - TEA - 2d - Fe y = -1,9134x + 51,66 R² =,563 22 23 24 25 26 1 C4654 - TEA - 28d - Fe y = -,4814x + 31,4 R² =,474 46 48 5 52 54 56 58 2,5 1,5 1,,5 C4654 - TEA - 1d - SR y = -,563x + 9,2234 R² =,8147 12,6 12,8 13 13,2 13,4 13,6 13,8 2,5 1,5 1,,5 C4654 - TEA - 2d - SR y = -,21x + 7,833 R² =,643 22 23 24 25 26 2,5 1,5 C4654 - TEA - 28d - SR 1, y = -,529x + 4,5852,5 R² =,4636 46 48 5 52 54 56 58 1 C4654 - TEA - 1d - AR y = 6,4131x - 78,953 R² =,9384 12,5 13 13,5 14 1 C4654 - TEA - 2d - AR y = 1,8956x - 39,99 R² =,3978 22 23 24 25 26 1 C4654 - TEA - 28d - AR y =,473x - 15,877 R² =,2443 46 48 5 52 54 56 58 Figure 2 Correlation between strength (MPa) and chemical composition of fly ashes (%) Clinker C4654, TEA
4 3 1 C4654 - TEA NaCl - 1d - Al y = 8,749x - 92,572 R² =,3963 14 14,2 14,4 14,6 14,8 15 15,2 4 3 1 C4654 - TEA NaCl - 2d - Al y = 3,8421x - 7,18 R² =,7471 23 24 25 26 27 4 3 1 C4654 - TEA NaCl - 28d - Al y =,7231x - 1,746 R² =,112 49 5 51 52 53 54 55 65 6 55 C4654 - TEA NaCl - 1d - Si y = -8,9924x + 189,82 R² =,529 5 14 14,2 14,4 14,6 14,8 15 15,2 8 6 C4654 - TEA NaCl - 2d - Si 4 y = -3,9913x + 157,58 R² =,8679 23 24 25 26 27 66 64 62 6 58 56 54 52 C4654 - TEA NaCl - 28d - Si y = -1,73x + 19,5 R² =,2339 49 5 51 52 53 54 55 1 C4654 - TEA NaCl - 1d - Fe y = -4,7912x + 76,283 R² =,512 14 14,2 14,4 14,6 14,8 15 15,2 1 C4654 - TEA NaCl - 2d - Fe y = -2,374x + 56,87 R² =,771 23 24 25 26 27 1 C4654 - TEA NaCl - 28d - Fe y = -,4297x + 27,766 R² =,1452 49 5 51 52 53 54 55 2,5 1,5 1,,5 C4654 - TEA NaCl - 1d - SR y = -,495x + 9,938 R² =,4431 14 14,2 14,4 14,6 14,8 15 15,2 2,5 1,5 1,,5 C4654 - TEA NaCl - 2d - SR y = -,2324x + 7,6385 R² =,8133 23,5 24 24,5 25 25,5 26 26,5 27 2,5 1,5 1,,5 C4654 - TEA NaCl - 28d - SR y = -,512x + 4,432 R² =,1673 49 5 51 52 53 54 55 1 C4654 - TEA NaCl - 1d - AR y = 3,882x - 51,623 R² =,242 14 14,5 15 15,5 1 C4654 - TEA NaCl - 2d - AR y = 2,1716x - 48,969 R² =,636 23,5 24 24,5 25 25,5 26 26,5 27 1 C4654 - TEA NaCl - 28d - AR y =,2788x - 8,7555 R² =,44 49 5 51 52 53 54 55 Figure 3 Correlation between strength (MPa) and chemical composition of fly ashes (%) Clinker C4654, TEA NaCl
4 3 1 C4654 - TEA NaSCN - 1d - Al y = 8,749x - 92,572 R² =,3963 14 14,2 14,4 14,6 14,8 15 15,2 4 3 1 C4654 - TEA NaSCN - 2d - Al y = 3,8421x - 7,18 R² =,7471 23,5 24 24,5 25 25,5 26 26,5 27 4 3 1 C4654 - TEA NaSCN - 28d - Al y =,7231x - 1,746 R² =,112 49 5 51 52 53 54 55 65 6 55 C4654 - TEA NaSCN - 1d - Si y = -4,777x + 13,2 R² =,4842 5 14 14,5 15 15,5 16 16,5 65 6 C4654 - TEA NaSCN - 2d - Si 55 y = -4,5238x + 172,87 R² =,967 5 24 24,5 25 25,5 26 26,5 27 8 6 4 C4654 - TEA NaSCN - 28d - Si y = -2,2863x + 174,23 R² =,8751 48 49 5 51 52 53 54 1 C4654 - TEA NaSCN - 1d - Fe y = -2,8275x + 49,347 R² =,5955 14 14,5 15 15,5 16 16,5 1 C4654 - TEA NaSCN - 2d - Fe y = -2,4529x + 68,342 R² =,9692 24 24,5 25 25,5 26 26,5 27 1 C4654 - TEA NaSCN - 28d - Fe y = -1,1748x + 65,763 R² =,7878 48 49 5 51 52 53 54 2,5 1,5 1,,5 C4654 - TEA NaSCN - 1d - SR y = -,2817x + 6,151 R² =,4791 14 14,5 15 15,5 16 16,5 2,5 1,5 1,,5 C4654 - TEA NaSCN - 2d - SR y = -,2756x + 8,843 R² =,9922 24 24,5 25 25,5 26 26,5 27 2,5 1,5 C4654 - TEA NaSCN - 28d - SR 1, y = -,1326x + 8,588,5 R² =,8136 48 49 5 51 52 53 54 1 C4654 - TEA NaSCN - 1d - AR y = 2,8532x - 38,472 R² =,4365 14 14,5 15 15,5 16 16,5 1 5, C4654 - TEA NaSCN - 2d - AR 1 y = 1,2255x - 57,87 R² =,6172 y = 2,947x - 68,63 R² =,9784 24 24,5 25 25,5 26 26,5 27 C4654 - TEA NaSCN - 28d - AR 48 49 5 51 52 53 54 Figure 4 Correlation between strength (MPa) and chemical composition of fly ashes (%) Clinker C4654, TEA NaSCN Table 4a reports R 2 linear correlation factor for the data referring to clinker C4564. Yellow color highlights strong correlations, while green is used for weaker, but still clearly visible, ones. Table 4a Clinker C4564 R 2 correlation factors Age Sample Al Si Fe SR AR 1 day blank.17.47.8.36.13 1 day TEA.846.741.749.815.938 1 day TEA NaCl.396.529.512.443.242 1 day TEA NaSCN.511.484.596.479.436 2 days blank.993.95.985.976.967 2 days TEA.525.684.563.64.398 2 days TEA NaCl.747.868.771.813.631 2 days TEA NaSCN.996.967.969.992.978 28 days blank.586.71.7.626.422
28 days TEA.392.558.474.464.244 28 days TEA NaCl.112.234.145.167.44 28 days TEA NaSCN.748.875.788.814.617 4.1.1 Blank For the cement prepared with this clinker, there is no correlation apparent at 24 hrs for the blank. At 2 days, strengths increase with higher Al content, and decrease with increasing Si and Fe. This is confirmed with SR (to which strength is inversely proportional) and AR (to which strength is directly proportional). At 28 days, correlation is definitely weaker, remaining visible in a more blurred way. 4.1.2 TEA The addition of TEA, with the exception of fly ash C4736, gives a general early strength increase. 28 days effect is rather neutral. In the presence of TEA, strengths develop a direct correlation at 1 day with Al content and AR; a weaker inverse correlation appears with Fe. Si by itself does not show a significant trend, but SR is inversely affecting strength on all spectrum. 4.1.3 TEA + NaCl The addition of chlorides, while enhancing considerably early strength on all the samples, tends to cancel out any effect of the chemical composition of the ashes. Correlations showed by the blank almost disappear (they are discernable only at 2 days), and the ones generated by the use of the single addition of TEA are no more visible. 4.1.4 TEA + NaSCN The different mechanism of action of thiocyanates (though not known) is evident through the fact that their correlation pattern is very different from the one showed by chlorides. A very strong strength increasing effect was recorded on all samples at 1 and 2 days. At 28 days this fades out or, in one case, a loss was found. Direct proportionality with Al content and AR is again evident at 2 and 28 days, as well as inverse proportionality to Si, Fe and SR, but not at 24 hrs, where the effectiveness of NaSCN is independent of these parameters. 4.2 Clinker C475 Strengths were plotted versus the chemical parameters and linear correlation equations were calculated. Graphs for each age and chemical parameter (along with the corresponding equations) are shown in Figures 5 to 8.
4 3 1 C475 - blank - 1d - Al y = 8,4642x - 86,879 R² =,6188 12,5 13 13,5 14 4 3 1 C475 - blank - 2d - Al y = 7,3931x - 141,31 R² =,3944 22 22,5 23 23,5 C475 - blank - 28d - Al 4y = 1,7417x - 57,273 3 R² =,7513 1 44 46 48 5 52 8 6 4 C475 - blank - 1d - Si y = -9,1173x + 179,35 R² =,7728 12,5 13 13,5 14 C475 - blank - 2d - Si 65 6 55 5 y = -5,82x + 189,38 22 R² 22,5 =,2631 23 23,5 C475 - blank - 28d - Si 66 64 62 6 58 56 y = -1,76x + 139,3 54 R² =,771 52 44 46 48 5 52 1 C475 - blank - 1d - Fe y = -4,6498x + 67,923 R² =,6853 12,5 13 13,5 14 1 C475 - blank - 2d - Fe y = -3,274x + 79,89 R² =,2832 22 22,5 23 23,5 1 C475 - blank - 28d - Fe y = -,8661x + 47,37 R² =,6818 44 46 48 5 52 2,5 1,5 1,,5 C475 - blank - 1d - SR y = -,5186x + 8,7416 R² =,6912 12,5 13 13,5 14 2,5 1,5 1,,5 C475 - blank - 2d - SR y = -,415x + 1,99 R² =,3461 22 22,5 23 23,5 2,5 1,5 C475 - blank - 28d - SR 1, y = -,132x + 6,7598,5 R² =,7851 44 46 48 5 52 1 C475 - blank - 1d - AR y = 4,523x - 54,956 R² =,4668 12,5 13 13,5 14 1 C475 - blank - 2d - AR y = 5,4167x - 117,28 R² =,5593 22 22,5 23 23,5 1 C475 - blank - 28d - AR y = 1,751x - 46,66 R² =,7563 44 46 48 5 52 Figure 5 Correlation between strength (MPa) and chemical composition of fly ashes (%) Clinker C475, blank
C475 - TEA - 1d - Al 4 3 y = 1,8348x +,5513 1 R² =,33 13,5 14 14,5 15 4 3 1 C475 - TEA - 2d - Al y = 7,929x - 16,6 R² =,9184 C475 - TEA - 28d - Al 4 y = 1,1351x - 28,441 3 R² =,2893 1 44 46 48 5 52 65 6 55 C475 - TEA - 1d - Si y = -3,3471x + 14,43 R² =,1183 5 13,5 14 14,5 15 8 6 C475 - TEA - 2d - Si 4 y = -7,1822x + 226,72 R² =,8112 C475 - TEA - 28d - Si 66 64 62 6 58 56y = -1,812x + 19,57 54 R² =,2825 52 44 46 48 5 52 1 C475 - TEA - 1d - Fe y = -1,3732x + 25,26 R² =,679 13,5 14 14,5 15 1 C475 - TEA - 2d - Fe y = -4,679x + 11,63 R² =,8871 1 C475 - TEA - 28d - Fe y = -,59x + 29,899 R² =,67 44 46 48 5 52 C475 - TEA - 1d - SR 2,5 1,5 1, y = -,1492x + 3,924 R² =,65,5 13,5 14 14,5 15 2,5 1,5 1,,5 C475 - TEA - 2d - SR y = -,4472x + 12,349 R² =,8695 2,5 1,5 1,,5 C475 - TEA - 28d - SR y = -,681x + 5,916 R² =,398 44 46 48 5 52 1 C475 - TEA - 1d - AR y =,1748x + 3,83 R² = 8 13,5 14 14,5 15 1 C475 - TEA - 2d - AR y = 4,9658x - 111,53 R² =,9517 1 C475 - TEA - 28d - AR y =,7696x - 31,592 R² =,3512 44 46 48 5 52 Figure 6 Correlation between strength (MPa) and chemical composition of fly ashes (%) Clinker C475, TEA
4 3 1 C475 - TEA NaCl - 1d - Al y = 8,1772x - 94,897 R² =,7296 14 14,5 15 15,5 4 3 1 C475 - TEA NaCl - 2d - Al y = 7,4157x - 149,5 R² =,8991 4 3 1 C475 - TEA NaCl - 28d - Al y = 3,421x - 121,37 R² =,6276 46 47 48 49 5 8 6 4 C475 - TEA NaCl - 1d - Si y = -8,772x + 177,15 R² =,7663 14 14,5 15 15,5 65 6 C475 - TEA NaCl - 2d - Si 55 y = -7,4422x + 233,41 R² =,9748 5 66 64 62 6 58 56 54 52 C475 - TEA NaCl - 28d - Si y = -3,2536x + 215,36 R² =,7727 46 47 48 49 5 1 C475 - TEA NaCl - 1d - Fe y = -4,85x + 66,293 R² =,6682 14 14,5 15 15,5 1 C475 - TEA NaCl - 2d - Fe y = -3,964x + 99,397 R² =,9411 1 C475 - TEA NaCl - 28d - Fe y = -1,6988x + 88,212 R² =,7183 46 47 48 49 5 2,5 1,5 1,,5 C475 - TEA NaCl - 1d - SR y = -,4873x + 9,291 R² =,779 14 14,5 15 15,5 2,5 1,5 1,,5 C475 - TEA NaCl - 2d - SR y = -,4388x + 12,183 R² =,9367 2,5 1,5 C475 - TEA NaCl - 28d - SR 1, y = -,1848x + 1,779,5 R² =,6893 46 47 48 49 5 1 C475 - TEA NaCl - 1d - AR y = 4,9985x - 68,564 R² =,72 14 14,5 15 15,5 1 C475 - TEA NaCl - 2d - AR y = 4,2533x - 95,51 R² =,7814 1 C475 - TEA NaCl - 28d - AR y = 1,675x - 72,56 R² =,463 46 47 48 49 5 Figure 7 Correlation between strength (MPa) and chemical composition of fly ashes (%) Clinker C475, TEA NaCl
4 3 1 C475 - TEA NaSCN - 1d - Al y = 8,1772x - 94,897 R² =,7296 14,2 14,4 14,6 14,8 15 15,2 15,4 15,6 4 3 1 C475 - TEA NaSCN - 2d - Al y = 7,4157x - 149,5 R² =,8991 4 3 1 C475 - TEA NaSCN - 28d - Al y = 3,421x - 121,37 R² =,6276 46 47 48 49 5 8 6 4 C475 - TEA NaSCN - 1d - Si y = -8,972x + 197,59 R² =,8469 15 15,5 16 16,5 65 6 55 C475 - TEA NaSCN - 2d - Si y = -4,3898x + 165,17 R² =,2743 5 23,5 24 24,5 25 25,5 8 6 4 C475 - TEA NaSCN - 28d - Si y = -2,7677x + 192,67 R² =,982 46 47 48 49 5 51 1 C475 - TEA NaSCN - 1d - Fe y = -4,9953x + 83,784 R² =,8951 15 15,5 16 16,5 1 C475 - TEA NaSCN - 2d - Fe y = -2,414x + 55,849 R² =,22 23,5 24 24,5 25 25,5 1 C475 - TEA NaSCN - 28d - Fe y = -1,592x + 79,496 R² =,98 46 47 48 49 5 51 2,5 1,5 1,,5 C475 - TEA NaSCN - 1d - SR y = -,5585x + 1,532 R² =,973 15 15,5 16 16,5 2,5 1,5 1,,5 C475 - TEA NaSCN - 2d - SR y = -,2782x + 8,6353 R² =,345 23,5 24 24,5 25 25,5 2,5 1,5 C475 - TEA NaSCN - 28d - SR 1, y = -,177x + 1,148,5 R² =,9549 46 47 48 49 5 51 1 C475 - TEA NaSCN - 1d - AR y = 6,1927x - 91,222 R² =,993 15 15,5 16 16,5 1 C475 - TEA NaSCN - 2d - AR y = 3,1852x - 72,659 R² =,3544 23,5 24 24,5 25 25,5 1 C475 - TEA NaSCN - 28d - AR y = 1,8514x - 84,947 R² =,9974 46 47 48 49 5 51 Figure 7 Correlation between strength (MPa) and chemical composition of fly ashes (%) Clinker C475, TEA NaSCN Table 4b reports R 2 linear correlation factor for the data referring to clinker C475. Yellow color highlights strong correlations, while green is used for weaker, but still clearly visible, ones. Table 4b Clinker C475 R 2 correlation factors Age Sample Al Si Fe SR AR 1 day blank.619.773.685.691.467 1 day TEA.33.118.68.65.1 1 day TEA NaCl.73.766.668.771.7 1 day TEA NaSCN.946.847.895.97.99 2 days blank.394.263.283.346.559 2 days TEA.918.811.887.87.952 2 days TEA NaCl.9.975.941.937.781 2 days TEA NaSCN.287.274.2.34.354 28 days blank.751.771.682.785.756
28 days TEA.289.282.7.31.351 28 days TEA NaCl.627.773.718.689.463 28 days TEA NaSCN.973.98.921.955.997 4.2.1 Blank In the case of clinker C475, the most evident correlation is with Si content: at all ages strength decreases with higher Si %. Weaker, but discernible inverse (Fe and SR) and direct (Al) correlations are present, but not at 2 days. 4.2.2 TEA TEA gives early strength increases and it s neutral at 28 days. Compared to the blank, the reaction pattern changes with the addition of TEA: 24 hrs and 28 days lose any correlation, while at 2 days all the parameters show some proportionality: direct for Al and AR, inverse for Si, Fe and SR. 4.2.3 TEA + NaCl Strong strength increase is shown at 24 hrs, less gain at 2 days, overly neutral at late ages. With NaCl, all parameters show correlations, at all ages. Direct for Al and AR, inverse for Si, Fe and SR. 4.2.4 TEA + NaSCN Strong to very strong strength increase is present at early ages, neutral effect at 28 days. This is the case of stronger correlation for this clinker; very evident at 24 hrs and 28 days for all the parameters, but not recordable at 2 days. 4.3 Comments on the results General considerations that can be made at this stage can be summarised as follows: -the presence of a chemical additive changes not only the absolute strength of tested cement, but also its way of reaction, since correlation to the same chemical parameters varies greatly; -though TEA was added in the same amount in all the addition tests, the presence of an inorganic salt changes again the picture very significantly, and the nature of such a salt plays a big role; -in the average, higher the amount of Al in the fly ash, higher are the strengths of the cement; however, the presence of a chemical additive tends to flatten out this effect by enhancing the strength to a similar level; -in the average, higher is the amount of Si in the fly ash, lower are the strengths of the cement. This correlation is relatively weak, though, and this effect is not normally seen as early as 24 hrs; -in the average, higher is the amount of Fe in the fly ash, lower are the strengths of the cement. This correlation is rather weak; -considerations above apply also to SR (inverse correlation) and AR (direct correlation); -in the case of addition of TEA by itself, the most important correlation seems to be with Al, then with Fe, while Si content is not particularly related to the reactivity; this is in accordance with the studies that show the effectiveness of TEA as a complexant for Al and Fe; -in the case of addition of TEA + NaCl, correlation pattern changes compared to TEA; it can be assumed that reaction mechanism should then be different; -in the case of addition of TEA + NaSCN, correlation pattern is again different, and normally stronger for the parameters considered compared to both TEA and TEA + NaCl;
-based on the last two above considerations, addition of TEA + NaCl should be the less sensitive strength enhancing addition to increase early strength of a blended fly ash cement, in the sense that it can give a gain in strength irrespective of the chemical composition of fly ashes. 5.Conclusions Additional work should be done on the subject to better understand the relation between chemical composition of fly ashes and their reactivity with chemical strength enhancers. At this stage, data collected can be a first step in better assessing the reaction mechanism of cement chemical additions, or at least in starting to build correlations between chemical parameters of blended cements and different additions. References Dodson V., 199. Concrete admixtures, Van Nostrand Reinhold, New York. Fraay A. L. A., 199. Fly ash, a pozzolan in concrete, PhD thesis, TU Delft. Gartner E., Myers D., 1993. Influence of tertiary alkanolamines on Portland cement hydration, J. Amer. Ceram. Soc., 76, 1521-153. Huettl, R.,. Der Wirkungsmechanismus von Steinkohlenflugasche als Betonzusatzstoff, PhD thesis, Bauingenieurwesen und Angewandte Geowissenschaften, TU Berlin. Kautz K., Prause B., 1986. Mineralogisch-chemische und technologische Eigenschaften von Steinkohlenflugaschen aus unterschiedlichen Feuerungen. VGB Kraftwerkstechnik, 66, 1194-1199. Lee C. Y., Lee H. K., Lee K. M., 3. Strength and microstructural characteristics of chemically activated fly ash-cement systems, Cem. Concr. Res. 33 (3), 425-431. Lutze D., vom Berg W. (ed.), 4. Handbuch Flugasche in Beton, Duesseldorf: Verlag Bau + Technik. Magistri M., Lo Presti A., 7. Influence of grinding aids, World Cement, 6, 39-41. Mueller H. S., Guse U., Schneider E., 5. Leistungfaehigkeit von Betonen mit Flugasche, Beton- und Stahlbetonbau, 1, 693-74. Prause B., 1991. Die Reaktion von Steinkohlen-Flugasche in hydraulisch und karbonatisch aushaertenden Bindemitteln. Kurzberichte aus der Bauforschung, 86, 629-633. Richartz W., 1984. Zusammensetzung und Eigenschafen von Flugaschen. Zement-Kalk-Gips, 37, 62-71. Sandberg P., 8. Effect of cement additives and chemical admixtures on cement hydration kinetics, Nanocem Articles, 1-4. Schulze S. E., Rickert J., 11. Influences of the chemical composition of fly ashes on their reactivity. In: Angel Palomo, Aniceto Zaragoza and Juan Carlos Lopez Aguì, ed. 13th International Congress on the Chemistry of Cement, Madrid 3-8 July 11.