XRD and Cements: from research to control quality

XRD and Cements: from research to control quality Ángeles G. De la Torre Lecturer of Inorganic Chemistry @ UMA ([email protected]) Dept. Química Inorgánica, Cristalografía y Mineralogía (UMA) Scientific Advisor @ X-Ray Data Services S.L. (www.xdataser.com) Spin off: X-Ray Data Services Research J. Appl. Cryst. (2016) 49, 722–735 Crystalline inorganic mixtures: A matrix of: [calcite (C) + gypsum (Gp) + quartz (Q)] + (0.00, 0.12, 0.25, 0.50, 1.0, 2.0 and 4.0 wt%) insoluble Anhydrite (i-A). 012345 0 1 2 3 4 5 i-Anhydrite Rietveld (wt%) Weighed (wt%) Mo-Kα 1 trm.Cu-Κα 1 refl. R 2 0.997 0.998 Slope 1.02(3) 1.05(2) Intercept 0.14(5) 0.14(4) The limit of quantification (LoQ) for a well crystallized inorganic phase could be established to be close to 0.12 wt% with good precision. However, the accuracy of these analyses was quite poor. Only contents >1.0 wt% yielded analyses with relative errors lower than 20%. J. Appl. Cryst. (2016) 49, 722–735 Research Limit of Quantification LoQ the minimum content you can obtain three times larger than its associated standard deviation. Crystalline inorganic mixtures: A matrix of: [calcite (C) + gypsum (Gp) + quartz (Q)] + (0.00, 0.12, 0.25, 0.50, 1.0, 2.0 and 4.0 wt%) insoluble Anhydrite (i-A). Limit of Detection LoD the minimum amount of the analyte yielding a powder pattern with its strongest (not overlapped) diffraction peak with an S/N larger than 3.0. i-A LoD MoKα1 0.3 wt% CuKα1 0.2 wt% XRPD laboratory > Applications > D8 ADVANCE (Bruker) J. Appl. Cryst. (2016) 49, 722–735 0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35 40 45 ACn (wt%) Weighed glass (wt%) Variable amorphous contents within an inorganic crystalline phase matrix: [calcite (C) + zincite (Z)] + (0, 2, 4, 8, 16 and 32 wt%) amorphous ground glass (Gl). Internal standard (20 wt% Quartz (Q)). Cu-Kα1 refl. Mo-Kα1 trm. Synchr. trm. Sample 0.0 wt% glass ACn /wt% Synchrotron 0.4(1) MoKα1 3.5(1) CuKα1 12.0(1) J. Appl. Cryst. (2016) 49, 722–735 Research MoKα1 results were more accurate Slope closer to 1.0 Small value in the amorphous free sample Good aggrement Cement research @ UMA > RQPA, CONSLUSIONS RQPA gives useful information for cements. (The answer will depend on the problem) Cement research @ UMA > eco-cements Clinkering kiln OPC Raw materials 78 wt% calcite 10 wt% kaolin 10 wt% quartz 2 wt% iron oxide BACSA Raw materials 69 wt% calcite 19 wt% kaolin 6 wt% quartz 3 wt% iron oxide 3 wt% gypsum OPC clinker Phases 65 wt% C3S 15 wt% C2S 10 wt% C4AF 10 wt% C3A BCSA clinker Phases 50 wt% C2S 30 wt% C4A3S 20 wt% C4AF 0.09 0.34 0.54 0.07 0.30 0.45 Electricity Fuel Raw materials 0.30 0.39 Electricity Fuel Raw materials OPC BACSA BCSA 0.07 BCSA Raw materials 59 wt% calcite 9 wt% kaolin 7 wt% quartz 17 wt% red bauxite 8 wt% gypsum BACSA clinker Phases 55 wt% C2S 15 wt% C3S 15 wt% C4A3S 15 wt% C4AF ~0.97 ~0.82 ~0.76 CSA Raw materials 35 wt% calcite 9 wt% kaolin 5 wt% red bauxite 26 wt% white bauxite 25 wt% gypsum CSA clinker Phases 65 wt% C4A3S 20 wt% C2S 6 wt% C4AF 9 wt% CS 0.26 CSA 1.00 t 0.28 0.07 ~0.61 Electricity Fuel Raw materials t CO2 / t clinker ~30% Al2O3approximate contents of the clinkers, wt%, just above ~17% ~6% ~11% BYF BAY BAY BYF BAY BYF 25 30 35 40 BAY_1 BAY_2 BAY_3 BAY_4 scBAY_4 1 43 2 1 1 1 4 4 4 33 3 33 33 3 333 5 333 3 3 333 333 3 3 3,6 3,6 3,6 3,6 3,6 3,6 333 3 333 3 3 3333 4 4 66 66 6 6 6 6 6 6 77 89 0 0 5 1 4 3,6 3,6 333 3 3 3333 4 6 6 67 2θ/ º Cement research @ UMA > eco-cements BAY Phase 1300ºC/15min with excess of sulfur* ß-C2S 59.4(2) γ-C2S 1.2(1) C4AF 6.5(2) CŜ 0.5(1) o-C4A3Ŝ 10.4(1) C3S 14.3(2) C12A7 4.5(1) Fluorellestadite 2.6(1) 0 1 2 3 4 5 6 7 8 9 0 5 10 15 20 25 Wt.% Time (hours) OPC-1 (0.0503g), w/c 0.45 C3S bC2S C4AF C3A Aft CsH1/2 CaCO3 CsH2 CH A (A+W) 0 1 2 3 4 5 6 7 8 9 0 5 10 15 20 25 Wt.% Time (hours) OPC-3 (0.213g), w/c 0.45 C3S bC2S C4AF C3A Aft CsH1/2 CaCO3 CsH2 CH A (A+W) D8 (Mo radiation) Transmission geometry + HUMIDITY CHAMBER + 2D DETECTOR Cement research @ UMA > Hydration and XRD 0 5 10 15 20 25 0 5 10 15 20 25 30 Wt.% Time (hours) oSK Anhydrite Aft C3S Strantlingite Amount of sample C3S AFt Anh Possible solution Sample between kapton in both sides Spinning (mandatory) Cement research @ UMA > Synchrotron XRD & hydration 0.04 0.06 0.08 0.10 0.12 0.14 0.16 senθ/λ(Å-1) t 0 18 h 31 h 2 d 7 d AFt: circle, AFm: star, C4A3S: square, Qz: triangle. st-C4A3S_1.16 recorded at different hydration ages Cement research @ UMA > Synchrotron XRD & hydration Cement research @ UMA > Synchrotron XRD & PDF Phases RQPA PDF-QPA Ca3Al2(OH)12 (crystalline) 43 wt% 42.0 wt% Al(OH)3·0.1H2O (nanocrystalline) 50 wt% 52.8 wt% 60 64 68 72 76 80 -0.6 -0.4 -0.2 0.0 0.2 0.4 4 8 12 16 20 24 28 -0.6 -0.3 0.0 0.3 0.6 32 36 40 44 48 52 56 60 -0.6 -0.3 0.0 0.3 0.6 2 3 4 5 -0.6 -0.3 0.0 0.3 0.6 G (r) (Å -2 ) (a) (b) G (r) (Å -2 ) G (r) (Å -2 ) r (Å) (c) (d) G (r) (Å -2 ) Cement research @ UMA > Synchrotron XRD & PDF 5 nm Cement research @ UMA > Synchrotron XRD & hydration Cement research @ UMA > Synchrotron XRD & hydration 2016-05-06 Spin off: X-Ray Data Services Provide support & advise Provide collaboration to research groups Provide advise -4 courses to companies with a diffractometer, (proper data collection, data analysis, validating their procedures), focus to control quality lab staff of cement factories (2) and pigment factories (2) - 3 courses to member of research groups @ Universities with diffractometers in their labs. - 2 specialized courses of XRD to control quality lab staff of cement factories and cement sector. - 1 specialized course to ceramic sector of Castellón (Spain) with 19 students. - 1 specialized course in customs central laboratory of the tax agency of Spain. X-Ray Data Services: training activity -Cement (anhydrous and paste) characterization. -RQPA of crystalline SiO2 in cements. -Hydration of cements: setting time. -Analysis of hardened precast. Data analysis activity X-Ray Data Services: data analysis activity Problem: Analysis of hardened precast concrete C3S peaks indicate unreacted cement in the surface area. Hydrated sample (grey line) shows a slight decrease of C3S, indicating that there was hydration. Sample M1: surface area of a precast concrete exposed to the sun. Sample M2: hydrated sample M1 (48 hours and dried with acetone). XRD and Cements: from research to control quality Ángeles G. De la Torre Lecturer of Inorganic Chemistry @ UMA ([email protected]) Dept. Química Inorgánica, Cristalografía y Mineralogía (UMA) Scientific Advisor @ X-Ray Data Services S.L. (www.xdataser.com)