Supporting materials of the manuscript submitted to Industrial & Engineering Chemistry Research Stability of Tricalcium Silicate and Other Primary Phases in Portland Cement Clinker Xuerun Li, Xiaodong Shen*, Mingliang Tang,Xiaodong Li State Key Laboratory of Materials-Oriented Chemical Engineering, College of Materials Science and Engineering, Nanjing Tech University, Nanjing, 210009, China AUTHOR INFORMATION * Corresponding author: Tel: +86-25-83587234; Fax: +86-25-83221690; E-mail: xdshen@njtech.edu.cn Contents 1. Polymorphs of the C 2 S 2. Avrami fitting of the kinetic data 3. Testing of another clinker on the decomposition temperature 4. Raw data of the manuscript 5. Processing of the kinetic data S1
1. Polymorphs of the C 2 S Figure. S1 and Figure. S2 give three plot of the PDFs of the C 2 S polymorphs, i.e. beta-c 2 S, gamma-c 2 S and alpha-c 2 S. Only the beta-c 2 S (Larnite) yields the best fit. Beta C 2 S f-cao Gamma C 2 S Figure. S1 Comparison of the gamma-c 2 S and the beta-c 2 S in our sample. Beta C 2 S f-cao Alpha C 2 S Figure. S2 Comparison of the alpha-c 2 S and the beta-c 2 S in our sample. 2. Avrami fitting of the kinetic data S2
Figure. S3 Avrami fitting of the decomposition of alite, herein, t is the reaction time (s) 3.Testing of another clinker on the decomposition temperature Taking the complicity of the industrial clinker, two different clinkers (clinker A and clinker B) were employed to find out the fastest decomposition temperature of C 3 S in clinker. Clinker B was just used to give a more universal temperature range of C 3 S. Most of the mechanism and kinetic research were done based on clinker A. Clinkers from cement plants (A : China United Cement Corporation, Xuzhou, Jiangsu Province, China; B: China United Cement Corporation, Nanjing, China) were used in our experiments. Table S1 Chemical composition of the clinker (%). Compositions a LOI b SiO 2 Al 2 O 3 Fe 2 O 3 CaO MgO SO 3 K 2 O c Na 2 O c Clinker A 0.77 20.78 5.73 3.49 64.76 3.02 0.34 0.62 0.10 Clinker B 1.42 20.05 5.42 3.37 65.10 2.27 0.68 0.49 0.23 a Compositions were determined per the methods specified in Chinese standard (GB/T 176-2008). b Loss on ignition at 950 C. c K 2 O and Na 2 O content was measured by the flame atomic absorption spectrometry (FAAS). Table S2 Mineral composition of the blank clinker (%) Clinker Method C 3 S C 2 S C 3 A C 4 AF f-cao f-mgo A Bogue 62.27 12.59 9.27 10.61 N/A N/A A XRD 59.27 19.64 13.94 5.00 0.60 1.51 B Bogue 71.46 3.57 8.65 10.24 N/A N/A B XRD 64.06 14.84 5.74 13.96 0.24 1.10 S3
The decomposition temperature is determined by the same method on clinker B (contour plot of C 3 S content is given in Figure S4), the resulted decomposition temperature is ~1150 C which is in agreement with the obtained temperature range for the decomposition of C 3 S (~1125-1150 C). Taking the chemical composition into consideration, both the clinker A and clinker B have similar composition. This is because the alkali contents and the sulfur consents are of the same level, which are considered as the factors governing the decomposition of C 3 S. When considering the decomposition temperature of C 3 S in clinker, both the sulfur and alkali content should be taken into consideration which could bring some shift of the decomposition temperature of C 3 S. Figure S4. Contour plot of the C 3 S content (%) of clinker B with time and temperature. S4
4. Raw data of the manuscript Table S3 f-cao content (%) determined using the XRD RIR method and using the chemical method Temp. a ( C) 1200 1159 1114 1042 1095 997 Time (h) XRD Chem. b XRD Chem. XRD Chem. XRD Chem. XRD Chem. XRD Chem. 0 2.45 1.97 2.27 1.98 1.43 0.931 1.74 1.61 1.21 1.08 0.5 3.4 2.35 4.45 3.227 4.86 4.544 3.59 3.22 3.88 3.368 1.92 1.444 1 3.7 2.61 5.31 4.096 5.81 5.714 5.12 4.78 5.32 5.331 2.52 1.926 3 4.4 3.23 8.19 7.4 8.83 8.42 7.03 6.86 8.41 8.2 4.4 4.167 7 -- -- -- -- 11.5 11.35 10.55 10.2 10.77 9.87 7.05 6.129 9 6.9 5.61 11.85 11.23 -- -- -- -- -- -- -- -- 13 7.7 6.69 13.55 13.08 13.62 12.92 12.73 12.45 13.69 13.22 9.32 9.11 21 9.3 7.75 15.16 14.31 15.22 15.04 15.03 14.62 14.79 14.55 11.14 10.98 37 10.7 8.53 17 16.54 16.38 16.15 15.68 15.35 15.85 15.3 12.97 12.45 60 11.1 8.99 16.84 16.28 16.91 16.48 16.76 16.28 16.92 16.48 14.51 14.05 a Temperature. b Chemical method. S5
Table S4 Mineral composition of clinker annealing at 915 o C obtained by XRD 0 55.77 22.63 13.41 5.37 1.06 1.71 0.5 55.57 22.27 13.49 5.57 1.08 1.97 1 54.09 23.30 13.42 5.69 1.27 2.18 3 50.25 25.36 14.78 5.66 1.77 2.14 7 49.58 25.71 14.87 5.09 2.56 2.16 13 46.46 27.02 15.68 5.14 3.39 2.24 21 42.20 29.75 16.23 5.62 3.95 2.18 37 41.88 30.11 15.97 5.32 4.41 2.26 60 38.70 32.18 15.94 5.47 5.12 2.54 Table S5 Mineral composition of clinker annealing at 965 o C obtained by XRD 0 55.99 21.69 5.40 14.23 1.10 1.91 0.5 54.73 22.24 5.39 14.51 1.46 1.91 1 53.47 22.78 5.38 14.80 1.81 1.92 3 49.11 25.09 5.33 15.49 3.08 2.06 7 41.77 30.22 5.40 15.15 5.12 2.18 13 32.47 36.58 5.32 16.12 7.05 2.25 21 26.08 40.94 5.49 16.44 8.47 2.25 37 20.67 44.56 5.58 16.49 10.11 2.23 60 17.20 45.90 5.66 17.29 11.71 2.22 Table S6 Mineral composition of clinker annealing at 997 o C obtained by XRD 0 55.79 21.48 14.15 5.39 1.21 1.93 0.5 53.94 22.13 14.27 5.53 1.92 2.15 1 51.77 23.24 15.04 5.38 2.52 2.00 3 45.12 27.53 15.48 5.29 4.40 2.1 7 33.57 36.07 15.48 5.71 7.05 2.09 13 23.40 42.89 16.6 5.41 9.32 2.35 21 16.75 47.41 16.76 5.66 11.14 2.27 37 10.45 51.34 17.04 5.90 12.97 2.29 60 8.60 51.34 17.61 5.83 14.51 2.11 Table S7 Mineral composition of clinker annealing at 1095 o C obtained by XRD 0 53.20 24.17 14.15 4.91 1.74 1.78 0.5 43.15 30.91 14.54 5.24 3.88 2.24 1 38.13 32.57 16.28 5.40 5.32 2.25 3 23.13 44.65 15.39 5.92 8.41 2.49 7 13.65 50.16 16.24 6.63 10.77 2.56 13 7.51 53.13 16.89 6.44 13.69 2.35 21 7.72 52.44 16.12 7.00 14.79 1.94 S6
37 5.37 53.41 16.45 7.06 15.85 1.87 60 4.90 53.15 16.49 6.70 16.92 1.84 Table S8 Mineral composition of clinker annealing at 1114 o C obtained by XRD 0.5 40.27 31.97 15.32 5.19 4.86 2.35 1 37.59 34.33 15.28 5.26 5.81 1.67 3 23.05 44.48 15.30 5.76 8.83 2.56 7 12.75 50.77 16.30 6.28 11.50 2.41 13 7.39 53.39 16.77 6.62 13.62 2.22 21 6.83 53.42 16.22 6.76 15.22 1.54 37 6.96 52.01 15.91 6.80 16.38 1.94 60 8.99 50.09 15.57 6.65 16.91 1.80 Table S9 Mineral composition of clinker annealing at 1159 o C obtained by XRD 0 51.91 25.57 13.8 4.62 2.27 1.76 0.5 41.57 30.61 14.63 5.69 4.45 2.99 1 37.53 32.89 15.09 5.86 5.31 3.26 3 25.48 40.85 15.71 6.36 8.19 3.37 9 14.30 47.38 16.56 6.72 11.85 3.15 13 9.10 51.15 15.80 7.07 13.55 3.33 21 8.11 51.93 15.51 7.26 15.16 2.03 37 7.57 49.97 15.82 7.11 17.00 2.54 60 12.45 45.37 15.56 7.62 16.84 2.16 Table S10 Mineral composition of clinker annealing at 1200 o C obtained by XRD. 0 50.96 26.39 13.68 4.84 2.45 1.62 0.5 44.70 29.60 14.60 5.70 3.40 2.10 1 42.90 30.90 14.40 6.00 3.70 2.00 3 40.20 31.60 15.10 6.30 4.40 2.40 9 29.60 40.50 14.20 6.70 6.90 2.10 13 26.20 42.20 14.40 7.40 7.70 2.10 21 23.60 42.50 15.30 7.10 9.30 2.00 37 23.30 40.10 16.90 6.70 10.70 2.20 60 22.90 37.10 20.40 6.20 11.10 2.20 S7
5. Processing of the kinetic data The treated parameter of the kinetic data was shown in k is the slop of the Jander model, which is also the rate constant of the reaction; K is the slope of the plot of ln k v.s. 1/T, the slope is obtained by the numerical differentiate method; the relation between the K v.s. Ea is defined by the Arrhenius equitation: Ea = -R K (Eq. (6) in the manuscript), herein K is the slope of to the temperature (T), as shown in Figure S5, so the Ea is also linear to the temperature. Table S11 Parameter of the kinetic data. T T 1/T k ln k K Ea K K -1 K mol kj mol -1 915 1188.12 8.42E-04 6.22E-08-1.66E+01-68421.65 568.86 965 1238.12 8.08E-04 6.37E-07-1.43E+01-54048.32 449.36 997 1270.12 7.87E-04 1.43E-06-1.35E+01-39515.80 328.53 1042 1315.12 7.60E-04 4.12E-06-1.24E+01-23069.12 191.80 1095 1368.12 7.31E-04 5.03E-06-1.22E+01-3727.19 30.99 1114 1387.12 7.21E-04 5.07E-06-1.22E+01 4426.14-36.80 1159 1432.12 6.98E-04 4.08E-06-1.24E+01 45068.77-374.70 1200 1473.12 6.79E-04 8.52E-07-1.40E+01 80612.51-670.21 Notes: (a) taken the positive value of the activation energy, all the K were treated to be minus. Figure S5 Numerical differentiation of the Arrhenius plot S8