Figure 1.
ESEM-BSE images of raw ground granulated blast-furnace slag ((GBFS) (left)) and fly ash ((FA) (right)) particles.
Figure 1.
ESEM-BSE images of raw ground granulated blast-furnace slag ((GBFS) (left)) and fly ash ((FA) (right)) particles.
Figure 2.
Particle size distributions of the studied GBFS and FA measured with Laser diffraction analyser.
Figure 2.
Particle size distributions of the studied GBFS and FA measured with Laser diffraction analyser.
Figure 3.
Quantitative phase analysis with the Rietveld method for the unreacted GBFS and FA. * stands for proportion of amorphous phase when excluding the internal standard in QXRD calculations.
Figure 3.
Quantitative phase analysis with the Rietveld method for the unreacted GBFS and FA. * stands for proportion of amorphous phase when excluding the internal standard in QXRD calculations.
Scheme 1.
Overall research flow.
Scheme 1.
Overall research flow.
Figure 4.
Monte Carlo simulation of the penetration of 1000 electrons accelerated at 15 kV in a beam radius of 10 nm into a GBFS (left) and the C-(N-)A-S-H gel (right). The red trajectories are back-scattered electrons, which result from elastic scattering events. Inelastic scattering events cause a reduction of electrons’ energy until the eventual disappearance in the specimen bulk. Yellow trajectories represent high-energy trajectories, and blue represents low-energy trajectories.
Figure 4.
Monte Carlo simulation of the penetration of 1000 electrons accelerated at 15 kV in a beam radius of 10 nm into a GBFS (left) and the C-(N-)A-S-H gel (right). The red trajectories are back-scattered electrons, which result from elastic scattering events. Inelastic scattering events cause a reduction of electrons’ energy until the eventual disappearance in the specimen bulk. Yellow trajectories represent high-energy trajectories, and blue represents low-energy trajectories.
Figure 5.
SEM-BSE image of the area of interest (3 × 3 matrix (fields are labelled 00–22), with an individual SI field comprising of 512 × 384 pixels) for paste microstructure characterization (sample is paste S50, unsealed cured for 28 days). All 9 fields of the area were analysed under the same analytical conditions. The total field width equals 750 microns.
Figure 5.
SEM-BSE image of the area of interest (3 × 3 matrix (fields are labelled 00–22), with an individual SI field comprising of 512 × 384 pixels) for paste microstructure characterization (sample is paste S50, unsealed cured for 28 days). All 9 fields of the area were analysed under the same analytical conditions. The total field width equals 750 microns.
Figure 6.
BSE image of the sample (left) and its corresponding PhAse Recognition and Characterization (PARC) phase map (middle). PARC legend (right) of different phases (groups) defined for the paste S50 (unsealed cured for 28 days) for the phase map (middle image).
Figure 6.
BSE image of the sample (left) and its corresponding PhAse Recognition and Characterization (PARC) phase map (middle). PARC legend (right) of different phases (groups) defined for the paste S50 (unsealed cured for 28 days) for the phase map (middle image).
Figure 7.
Large area BSE image of a polished section of an epoxy-impregnated unreacted GBFS (the number of acquired fields was 9). The image width is 768 µm.
Figure 7.
Large area BSE image of a polished section of an epoxy-impregnated unreacted GBFS (the number of acquired fields was 9). The image width is 768 µm.
Figure 8.
PARC sum spectrum for a GBFS particle (purple coloured in the PARC map,
Figure 9), indicating the presence of Mg, Al, Si, S, and Ca by their characteristic X-ray lines.
Figure 8.
PARC sum spectrum for a GBFS particle (purple coloured in the PARC map,
Figure 9), indicating the presence of Mg, Al, Si, S, and Ca by their characteristic X-ray lines.
Figure 9.
Large-area PARC phase map of the unreacted GBFS ((left) (image width: 768 µm)) and the legend of group phases identified in the unreacted GBFS (right).
Figure 9.
Large-area PARC phase map of the unreacted GBFS ((left) (image width: 768 µm)) and the legend of group phases identified in the unreacted GBFS (right).
Figure 10.
Large-area BSE image of a polished section of an epoxy-impregnated unreacted FA (the number of acquired fields was 12). The image width is 1024 µm.
Figure 10.
Large-area BSE image of a polished section of an epoxy-impregnated unreacted FA (the number of acquired fields was 12). The image width is 1024 µm.
Figure 11.
PARC sum spectra for AlSi pixels (blue coloured in the composite map,
Figure 12) and Quartz (SiO
2, yellow coloured in the composite map,
Figure 12), indicating the presence of O, Al, and Si by their characteristic X-ray lines.
Figure 11.
PARC sum spectra for AlSi pixels (blue coloured in the composite map,
Figure 12) and Quartz (SiO
2, yellow coloured in the composite map,
Figure 12), indicating the presence of O, Al, and Si by their characteristic X-ray lines.
Figure 12.
Large-area PARC phase image with individual phases in unreacted FA (width 1024 µm) (left); legend of identified phases (right).
Figure 12.
Large-area PARC phase image with individual phases in unreacted FA (width 1024 µm) (left); legend of identified phases (right).
Figure 13.
SEM-BSE images of the S100 microstructure (sealed cured paste for 28 days) and the compound domains of different phases.
Figure 13.
SEM-BSE images of the S100 microstructure (sealed cured paste for 28 days) and the compound domains of different phases.
Figure 14.
PARC sum spectra for compound domains of slag particles, NaAlSiCa gel, and NaMgAlSiCa gel in paste S100.
Figure 14.
PARC sum spectra for compound domains of slag particles, NaAlSiCa gel, and NaMgAlSiCa gel in paste S100.
Figure 15.
SEM-BSE images (a–f-i) of of paste S100’s microstructure at different curing periods, with mapped compound domains of the different phases (a–f-ii). Image width = 250 µm.
Figure 15.
SEM-BSE images (a–f-i) of of paste S100’s microstructure at different curing periods, with mapped compound domains of the different phases (a–f-ii). Image width = 250 µm.
Figure 16.
The BSE image of the microstructure around a reacted GBFS particle of the paste S100 after 1 year of reaction (left) and corresponding EDX linescan-profiles along the yellow arrow for the constituent elements (Si, O, Ca, Al, Mg, Na) (right).
Figure 16.
The BSE image of the microstructure around a reacted GBFS particle of the paste S100 after 1 year of reaction (left) and corresponding EDX linescan-profiles along the yellow arrow for the constituent elements (Si, O, Ca, Al, Mg, Na) (right).
Figure 17.
(a) Density plot of Na and (Mg + Al + Si + Ca) to extract groups of pixels for Ca-Na-Al-Si gel and Ca-Mg-Na-Al-Si gel in paste S100, sealed cured for 28 days; (b) Density plot of Na and (Mg + Al + Si + Ca) to extract groups of pixels for Ca-Na-Al-Si gel and Ca-Mg-Na-Al-Si gel in paste S100 cured and sealed for 28 days.
Figure 17.
(a) Density plot of Na and (Mg + Al + Si + Ca) to extract groups of pixels for Ca-Na-Al-Si gel and Ca-Mg-Na-Al-Si gel in paste S100, sealed cured for 28 days; (b) Density plot of Na and (Mg + Al + Si + Ca) to extract groups of pixels for Ca-Na-Al-Si gel and Ca-Mg-Na-Al-Si gel in paste S100 cured and sealed for 28 days.
Figure 18.
The effect of curing conditions (unsealed and sealed) on the evolution of the phases and their weight proportions in paste S100.
Figure 18.
The effect of curing conditions (unsealed and sealed) on the evolution of the phases and their weight proportions in paste S100.
Figure 19.
PARC sum spectrum from compound domain of CaAlSi gel, CaNaAlSi gel, and CaMgNaAlSi gel in S50.
Figure 19.
PARC sum spectrum from compound domain of CaAlSi gel, CaNaAlSi gel, and CaMgNaAlSi gel in S50.
Figure 20.
SEM-BSE images (a–f-i) of the microstructure of paste S50 at different curing periods, with mapped compound domains of different phases (a–f-ii). Image width = 250 µm.
Figure 20.
SEM-BSE images (a–f-i) of the microstructure of paste S50 at different curing periods, with mapped compound domains of different phases (a–f-ii). Image width = 250 µm.
Figure 21.
The effect of curing conditions (unsealed and sealed) on the evolution of the phases and their weight proportions in pastes S50. Note that AlSi grain includes all FA phases.
Figure 21.
The effect of curing conditions (unsealed and sealed) on the evolution of the phases and their weight proportions in pastes S50. Note that AlSi grain includes all FA phases.
Figure 22.
Degree of reaction of paste S100 (left) and paste S50 (right).
Figure 22.
Degree of reaction of paste S100 (left) and paste S50 (right).
Figure 23.
XRD diffractograms showing the phases in paste S50 for sealed and unsealed curing conditions.
Figure 23.
XRD diffractograms showing the phases in paste S50 for sealed and unsealed curing conditions.
Figure 24.
Quantitative phase analysis with the Rietveld method for paste S50 as a function of time and curing conditions. * stands for proportion of amorphous phase when excluding the internal standard in QXRD calculations.
Figure 24.
Quantitative phase analysis with the Rietveld method for paste S50 as a function of time and curing conditions. * stands for proportion of amorphous phase when excluding the internal standard in QXRD calculations.
Table 1.
Chemical compositions of FA and GBFS measured with XRF (%).
Table 1.
Chemical compositions of FA and GBFS measured with XRF (%).
- | Na2O | MgO | Al2O3 | SiO2 | P2O5 | S | K2O | CaO | TiO2 | Fe2O3 | L.O.I. |
---|
FA | 0.8 | 1.5 | 23.8 | 56.8 | 0.5 | 0.3 | 1.6 | 4.8 | 1.2 | 7.2 | 1.2 |
GBFS | 0.4 | 8.0 | 13.5 | 35.5 | 0.0 | 1.0 | 0.5 | 39.8 | 1.0 | 0.6 | −1.3 |
Table 2.
Mixture design for pastes with respect to 100 g of binder.
Table 2.
Mixture design for pastes with respect to 100 g of binder.
Mixture | FA a | GBFS b | m(Na2O)/ m(binder) | SiO2/ Na2O | Water | Activator | Curing Regime |
---|
S50 | 50 | 50 | 4.80 | 1.45 | 38.00 | 12.00 | Unsealed/ Sealed |
S100 | 0 | 100 |
Table 3.
Chemical composition of GBFS obtained with PARC (wt%).
Table 3.
Chemical composition of GBFS obtained with PARC (wt%).
- | Na2O | MgO | Al2O3 | SiO2 | P2O5 | SO3 | K2O | CaO | TiO2 | MnO | Fe2O3 |
---|
GBFS | 0.45 | 8.14 | 13.09 | 35.48 | 0.22 | 2.53 | 0.35 | 38.11 | 1.12 | 0.32 | 0.19 |
Table 4.
Chemical composition of phase domains of FA particles obtained with PARC (wt%).
Table 4.
Chemical composition of phase domains of FA particles obtained with PARC (wt%).
- | Density (g/cm3) | Weight Avg | Na2O | MgO | Al2O3 | SiO2 | P2O5 | SO3 | K2O | CaO | TiO2 | MnO | Fe2O3 |
---|
Quartz (SiO2) | 2.62 | 8.50 | 0.31 | 0.09 | 0.09 | 98.35 | 0.14 | 0.63 | 0.00 | 0.00 | 0.00 | 0.00 | 0.39 |
Hematite and Magnetite 1 | 5.74 | 0.97 | 0.33 | 0.46 | 0.76 | 3.04 | 0.00 | 0.00 | 0.20 | 0.59 | 0.00 | 0.36 | 94.27 |
AlSi_grain | 2.44 | 76.21 | 0.88 | 0.64 | 31.51 | 58.67 | 0.48 | 0.26 | 1.74 | 0.87 | 1.11 | 0.03 | 6.37 |
NaAlSi_grain | 2.44 | 1.91 | 5.36 | 0.78 | 25.58 | 61.24 | 0.57 | 0.16 | 2.03 | 0.60 | 0.58 | 0.2 | 2.90 |
KAlSi_grain | 2.44 | 1.51 | 1.07 | 0.20 | 19.82 | 66.40 | 0.31 | 0.20 | 10.45 | 0.30 | 0.30 | 0.03 | 0.95 |
CaAlSi_grain | 2.44 | 2.51 | 0.00 | 0.37 | 35.18 | 41.74 | 0.70 | 0.15 | 0.00 | 17.45 | 0.56 | 0.00 | 3.85 |
MgAlSi_grain | 2.44 | 1.99 | 1.07 | 9.44 | 20.28 | 57.13 | 0.78 | 0.14 | 1.22 | 1.25 | 0.61 | 0.16 | 7.94 |
FeAlSi_grain | 2.44 | 0.92 | 0.56 | 1.04 | 14.60 | 39.80 | 0.23 | 0.05 | 0.98 | 0.71 | 1.12 | 0.05 | 40.85 |
TiAlSi_grain | 2.44 | 0.86 | 1.27 | 1.22 | 29.71 | 43.39 | 0.00 | 0.00 | 1.51 | 2.77 | 14.45 | 1.24 | 4.45 |
CaMgAlSi_grain | 2.44 | 1.27 | 0.14 | 8.24 | 20.64 | 39.17 | 2.34 | 0.00 | 0.02 | 21.03 | 0.53 | 0.11 | 7.78 |
MgFe_grain | 2.44 | 1.47 | 0.01 | 6.67 | 1.86 | 0.57 | 0.04 | 0.03 | 0.01 | 0.39 | 0.11 | 0.81 | 89.51 |
P_grain | 2.44 | 0.93 | 0.00 | 6.09 | 11.6 | 17.14 | 24.01 | 0.07 | 0.30 | 36.60 | 0.88 | 0.00 | 3.31 |
Calcite (CaCO3) | 2.71 | 0.29 | 0.00 | 0.00 | 0.82 | 0.43 | 1.54 | 2.33 | 0.00 | 94.38 | 0.00 | 0.00 | 0.49 |
Dolomite (CaMg(CO3)2) | 2.87 | 0.12 | 0.00 | 32.17 | 1.30 | 2.09 | 0.97 | 3.75 | 0.07 | 57.65 | 0.09 | 0.14 | 1.78 |
Al2O3 | 4.00 | 0.54 | 0.08 | 0.00 | 91.84 | 5.37 | 0.45 | 0.02 | 0.07 | 0.31 | 1.02 | 0.02 | 0.84 |
Table 5.
Chemical composition of FA obtained with PARC (wt%).
Table 5.
Chemical composition of FA obtained with PARC (wt%).
- | Na2O | MgO | Al2O3 | SiO2 | P2O5 | SO3 | K2O | CaO | TiO2 | MnO | Fe2O3 |
---|
FA | 1.05 | 1.13 | 24.99 | 60.46 | 0.59 | 0.38 | 1.70 | 2.21 | 1.41 | 0.06 | 6.02 |
Table 6.
Atomic ratios in the reaction products by PARC analysis in pastes S100.
Table 6.
Atomic ratios in the reaction products by PARC analysis in pastes S100.
Paste S100 |
---|
Reaction products | CaNaAlSi | CaMgNaAlSi | CaAlSi |
Atomic ratio | Na/Si | Mg/Si | Al/Si | Ca/Si | Na/Si | Mg/Si | Al/Si | Ca/Si | Na/Si | Al/Si | Ca/Si |
Standard deviation | ±0.003 | ±0.001 | ±0.003 | ±0.016 | ±0.020 | ±0.017 | ±0.002 | ±0.025 | ±0.007 | ±0.006 | ±0.027 |
1 day sealed | 0.37 | 0.11 | 0.25 | 0.61 | 0.43 | 0.34 | 0.36 | 0.45 | − | − | − |
7 days sealed | 0.37 | 0.11 | 0.27 | 0.64 | 0.31 | 0.53 | 0.46 | 0.66 | − | − | − |
28 days sealed | 0.33 | 0.10 | 0.26 | 0.84 | 0.31 | 0.66 | 0.52 | 0.84 | − | − | − |
1 year sealed | 0.29 | 0.10 | 0.24 | 0.85 | 0.25 | 0.69 | 0.51 | 0.83 | − | − | − |
7 days unsealed | 0.32 | 0.10 | 0.26 | 0.60 | 0.27 | 0.49 | 0.44 | 0.61 | − | − | − |
28 days unsealed | 0.12 | 0.11 | 0.25 | 0.69 | 0.08 | 0.41 | 0.40 | 0.73 | 0.06 | 0.18 | 0.71 |
Table 7.
Atomic ratios in the reaction products by PARC analysis in paste S50.
Table 7.
Atomic ratios in the reaction products by PARC analysis in paste S50.
Paste S50 |
---|
Reaction products | CaNaAlSi | CaMgNaAlSi | CaAlSi |
Atomic ratio | Na/Si | Mg/Si | Al/Si | Ca/Si | Na/Si | Mg/Si | Al/Si | Ca/Si | Na/Si | Al/Si | Ca/Si |
Standard deviation | ±0.002 | ±0.002 | ±0.002 | ±0.007 | ±0.033 | ±0.027 | ±0.011 | ±0.024 | ±0.001 | ±0.002 | ±0.002 |
1 day sealed | 0.33 | 0.10 | 0.26 | 0.30 | 0.35 | 0.29 | 0.32 | 0.28 | 0.19 | 0.30 | 0.37 |
7 days sealed | 0.35 | 0.08 | 0.29 | 0.34 | 0.41 | 0.37 | 0.45 | 0.41 | 0.19 | 0.35 | 0.47 |
28 days sealed | 0.30 | 0.09 | 0.31 | 0.49 | 0.33 | 0.30 | 0.37 | 0.49 | 0.18 | 0.36 | 0.46 |
1 year sealed | 0.40 | 0.05 | 0.30 | 0.50 | 0.47 | 0.37 | 0.38 | 0.51 | 0.11 | 0.55 | 0.35 |
7 days unsealed | 0.30 | 0.08 | 0.28 | 0.33 | 0.41 | 0.29 | 0.43 | 0.31 | 0.16 | 0.29 | 0.38 |
28 days unsealed | 0.25 | 0.09 | 0.30 | 0.48 | 0.26 | 0.28 | 0.35 | 0.47 | 0.14 | 0.31 | 0.49 |
Table 8.
Bulk chemistry obtained with XRF for the paste S100.
Table 8.
Bulk chemistry obtained with XRF for the paste S100.
S100 | 1 Day Sealed | 7 Days Sealed | 28 Days Sealed | 1 Year Sealed | 7 Days Unsealed | 28 Days Unsealed |
---|
Na2O | 4.48 | 4.80 | 4.45 | 5.12 | 3.96 | 2.76 |
MgO | 6.00 | 6.11 | 5.89 | 6.71 | 6.29 | 6.02 |
Al2O3 | 10.09 | 10.35 | 9.98 | 10.02 | 10.59 | 10.32 |
SiO2 | 33.90 | 34.70 | 33.71 | 36.42 | 35.44 | 34.58 |
P2O5 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
S | 1.44 | 1.44 | 1.43 | 1.60 | 1.32 | 1.20 |
K2O | 0.42 | 0.41 | 0.42 | 0.33 | 0.40 | 0.38 |
CaO | 40.53 | 39.62 | 41.24 | 37.40 | 39.29 | 41.76 |
TiO2 | 1.39 | 1.22 | 1.40 | 1.17 | 1.31 | 1.43 |
MnO | 0.36 | 0.31 | 0.35 | 0.32 | 0.33 | 0.38 |
Fe2O3 | 0.69 | 0.66 | 0.68 | 0.61 | 0.66 | 0.67 |
Table 9.
Bulk chemistry obtained with XRF for the paste S50.
Table 9.
Bulk chemistry obtained with XRF for the paste S50.
S50 | 1 Day Sealed | 7 Days Sealed | 28 Days Sealed | 1 Year Sealed | 7 Days Unsealed | 28 Days Unsealed |
---|
Na2O | 5.09 | 5.12 | 4.46 | 4.56 | 4.78 | 3.88 |
MgO | 3.87 | 4.07 | 3.78 | 4.16 | 4.21 | 4.50 |
Al2O3 | 15.42 | 15.08 | 13.71 | 14.41 | 15.36 | 15.49 |
SiO2 | 43.27 | 43.38 | 41.00 | 45.74 | 44.12 | 44.83 |
P2O5 | 0.31 | 0.32 | 0.30 | 0.23 | 0.32 | 0.34 |
S | 1.07 | 1.10 | 1.17 | 1.12 | 1.00 | 0.96 |
K2O | 0.85 | 0.86 | 0.93 | 0.81 | 0.82 | 0.80 |
CaO | 22.50 | 22.92 | 25.89 | 22.58 | 22.39 | 22.47 |
TiO2 | 1.34 | 1.36 | 1.59 | 1.30 | 1.26 | 1.34 |
MnO | 0.20 | 0.21 | 0.26 | 0.21 | 0.20 | 0.21 |
Fe2O3 | 4.94 | 4.82 | 6.03 | 4.73 | 4.65 | 4.58 |
Table 10.
Bulk chemistry obtained with PARC for the paste S100.
Table 10.
Bulk chemistry obtained with PARC for the paste S100.
S100 | 1 Day Sealed | 7 Days Sealed | 28 Days Sealed | 1 Year Sealed | 7 Days Unsealed | 28 Days Unsealed |
---|
Na2O | 4.71 | 4.92 | 4.90 | 4.35 | 4.32 | 1.77 |
MgO | 7.03 | 7.10 | 6.82 | 7.17 | 7.15 | 6.68 |
Al2O3 | 12.09 | 12.06 | 11.51 | 10.84 | 12.26 | 11.60 |
SiO2 | 30.04 | 31.03 | 33.62 | 33.87 | 31.06 | 33.49 |
P2O5 | 0.32 | 0.30 | 0.24 | 0.24 | 0.31 | 0.31 |
SO3 | 1.68 | 1.95 | 1.72 | 1.66 | 1.60 | 1.24 |
K2O | 0.54 | 0.47 | 0.36 | 0.31 | 0.48 | 0.34 |
CaO | 41.09 | 40.44 | 39.22 | 39.80 | 41.23 | 42.95 |
TiO2 | 1.01 | 0.99 | 1.02 | 1.01 | 1.03 | 1.03 |
MnO | 0.29 | 0.29 | 0.29 | 0.29 | 0.30 | 0.28 |
Fe2O3 | 0.40 | 0.44 | 0.31 | 0.48 | 0.25 | 0.33 |
Table 11.
Bulk chemistry obtained with PARC for the paste S50.
Table 11.
Bulk chemistry obtained with PARC for the paste S50.
S50 | 1 Day Sealed | 7 Days Sealed | 28 Days Sealed | 1 Year Sealed | 7 Days Unsealed | 28 Days Unsealed |
---|
Na2O | 4.26 | 4.54 | 4.13 | 6.49 | 3.61 | 2.55 |
MgO | 4.83 | 5.13 | 4.51 | 4.42 | 5.26 | 4.84 |
Al2O3 | 16.46 | 17.41 | 17.06 | 15.21 | 16.87 | 16.30 |
SiO2 | 42.88 | 42.55 | 40.30 | 44.23 | 43.22 | 43.21 |
P2O5 | 0.61 | 0.61 | 0.55 | 0.55 | 0.61 | 0.55 |
SO3 | 1.22 | 1.40 | 1.85 | 1.71 | 1.46 | 1.62 |
K2O | 1.09 | 1.05 | 1.00 | 0.98 | 1.03 | 0.84 |
CaO | 23.77 | 23.44 | 26.83 | 22.69 | 23.80 | 26.73 |
TiO2 | 0.94 | 1.03 | 0.91 | 0.98 | 1.05 | 0.91 |
MnO | 0.21 | 0.19 | 0.17 | 0.23 | 0.21 | 0.20 |
Fe2O3 | 3.71 | 2.39 | 2.44 | 2.61 | 2.90 | 2.24 |