quantitative powder diffraction analyses of cements · s alite: 7 polymorphs with temperature...
TRANSCRIPT
Miguel A. G. Aranda
Departamento de Química Inorgánica, Universidad de Málaga, Spain
Quantitative powder
diffraction analyses of cements
Outline: QPA of cementsOutline: QPA of cements
1.
Introduction: the uses of powder diffraction
3.
Analytical method validation
7.
Conclusions
4. Polymorph determination
2.
Introduction: synchrotron radiation
5. Portland clinkers and cements
6. In-situ study of belite clinkering
Introduction: XRPD applications
# 1 Identification of crystalline compounds (using the PDF database). (Based on Ihkl
and dhkl
)
# 2 Determination of the unit cell parameters.
(Based on dhkl
)
# 3 Determination of the crystal structure (atomic parameters).
(Based on Ihkl
and dhkl
)
# 4 Quantitative phase analysis (sample purity).
(Based on Ihkl
)
# 5 Determination of the microstructure of the phase. (Based on the shape-‘FWHM’
of the Ihkl
)(average microparticle
size and shape, microstrains, residual stress, etc.)
# 6 XRPD can be coupled to thermal variation (thermodiffractometry):Uses for: phase transitions, chemical reactions, melting/crystallization, thermal expansion, …
# 7,8,9, …
XRPD coupled to pressure, chemical gradient, magnetic fields, …; and combinations:
Uses for: phase transitions, equation of state determination, reactivity, stability, …
Chalk phase identification
Pdf•identification
# 1 Identification of crystalline compounds
CaSO4.2H2 O
CaCO3
Forensic Science Laboratory of Stuttgart, Germany
# 1 Identification of crystalline mixtures
Ca3-x Mgx SiO5 , main cement phase, x=0.00, 0.02, 0.04, 0.06, 0.08 and 0.10. The figure shows the evolution in the peak positions, consequence of the evolution of the unit cell parameters. Important for reactivity (water hydration / hardening).
# 2 Determination of the unit cell parameters.
28 30 32 34 36 38 40
2
I (u.
a)
0Mg
02Mg
04Mg
06Mg
08Mg
1Mg
# 3 Determination of the crystal structure (atomic parameters)
Reaction of MgO-Al2
O3
followed by XRPD
XRPD of a pure phase
# 4 Quantitative phase analysis (sample purity)
XRPD of a pure phase
XRPD of a pure phase
XRPD of a mixture
XRPD of a mixture
Elemental analysis
XRF, the same
# 4 Quantitative phase analysis (sample purity)
Sources of peak broadening
Instrumental BroadeningInstrumental Broadening
A antiphase
domainB interstitial atomG, K grain boundaryL vacancyS substitutional
impurity/dopingS’
interstitial impurityP, Z stacking faults┴
dislocations
Microstructural featuresMicrostructural features
2 θ (º)2 θ (º)Finite Crystallite Size
FWHM α
cos-1
θ
(if
isotropic)size
< 0.2 μm
Lattice Strain (microstrain)
FWHM α
tan θ
(if
isotropic)fluctuations in cell parameters
Extended Defects
Anisotropic broadeningAntiphase
Boundaries, Stacking Faults
# 5 Determination of the microstructure of the phase
# 5 Determination of the microstructure of the phase
CeO2 standard;a=5.412058(6) Å;GSAS, S/L=H/L=0.012;GU=1.95(-); GW= 2.31(2); LX=0.90(2); LY=2.56(4);Rwp=4.55%
CeO2 standard;a=5.412058(6) Å;GSAS, S/L=H/L=0.012;GU=1.95(-); GW= 2.31(2); LX=0.90(2); LY=2.56(4);Rwp=4.55%
CeO2 nano;a=5.412229(9) Å;GSAS, S/L=H/L=0.012;GU=1.95(-); GW= 2.73(-); LX=24.90(3); LY=32.63(6);Rwp=5.9%
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
0.0060
0.0065
0.0070
Parameter Value Error------------------------------------------------------------A 0.00572 4.80898E-5B 3.70184E-4 1.86547E-5------------------------------------------------------------
R SD N P------------------------------------------------------------0.9851 5.66378E-5 14 <0.0001------------------------------------------------------------
(na
no-
std)·c
os
4sen
DV = 269 Å ó 27(1) nm str = 0.037(2)%
Top:
Experimental setup for high-resolution SXRP-thermodiffraction using a hot-air blower at ID31 diffractometer of ESRF.
18.0 18.4 18.8 19.2 19.6873
973
1073
1173
2/º
T/K
(a)
18.0 18.4 18.8 19.2 19.6873
973
1073
1173
2/º
T/K
(a)
Bottom right: Selected HT-SXRPD patterns for La9.75
0.25
(Ge6
O24
)O2.62
showing a triclinic-to-
hexagonal phase transition.
Bottom left: Variation of the unit cell volume
# 6 XRPD can be coupled to thermal variation (thermodiffractometry)
250 500 750 1000 1250
620
624
628
632
636
V/Å
3
T/K
(b)
250 500 750 1000 1250
620
624
628
632
636
V/Å
3
T/K
(b)
# 7 In-situ chemical reactivity study (hydration of a cement)
2D single pattern
X-Rays
Slit Slit
~ 5 min/pattern
2D single pattern
X-Rays
Slit Slit
~ 5 min/patternX-Rays
Slit Slit
X-Rays
SlitSlit SlitSlit
~ 5 min/pattern
Image plate detector: two data collection strategies Translating mode
Sample
~2 mm
SlitSlit
~ 5 min time resolutionX-Rays
Translating mode
Sample
~2 mm
SlitSlit
~ 5 min time resolutionX-Rays
~2 mm
SlitSlitSlit
~ 5 min time resolutionX-Rays
Integration Fit2D
Outline: QPA of cementsOutline: QPA of cements
1.
Introduction: the uses of powder diffraction
3.
Analytical method validation
7.
Conclusions
4. Polymorph determination
2.
Introduction: synchrotron radiation
5. Portland clinkers and cements
6. In-situ study of belite clinkering
Bending magnetInsertion devices:
undulators & wigglers
1. The high resolution decreases the peak overlapping
2. In transmission , a large amount of sample is tested (
=2 mm)
4. Preferred orientation is almost absent
3. The absorption and microabsorption
problems are minimal
Advantages of synchrotron radiation
Disadvantages of synchrotron radiation vs. laboratory data
The patterns are much more expensive
A compromise in some cases: Strictly monochromatic X-ray laboratory data (CuK1 )
5. Very high intensities (very short counting times !)
C3SC
4A
F
CaS
O4
2H2O
CaS
OC
aSO
442H2
H22OO
CaS
O4
½H
2O
C3SC
4A
F
CaS
O4
2H2O
CaS
OC
aSO
442H2
H22OO
CaS
O4
½H
2O
C3S
C4A
F
C3A
C3A
)
CaS
O4
2H2O
CaS
OC
aSO
44 2
H2H
22OO
CaS
O4
½H
2O
C3S
C4A
F
C3A
C3A
)
CaS
O4
2H2O
CaS
OC
aSO
44 2
H2H
22OO
CaS
O4
½H
2OSynchrotron patterncapillary
Laboratory patternflat
Two patterns of the sameartificial cement
1.- High resolution2.- No preferred orientation3.- Good s/n ratio(4.- Good particle statistic)
Outline: QPA of cementsOutline: QPA of cements
1.
Introduction: the uses of powder diffraction
3.
Analytical method validation
7.
Conclusions
4. Polymorph determination
2.
Introduction: synchrotron radiation
5. Portland clinkers and cements
6. In-situ study of belite clinkering
Ordinary Portland cement, OPC
Set time controller
CaSO4 ·2H2 O (gypsum) others,… CaSO4 ·½H2 O (bassanite)CaSO4 (anhydrite)
Additions CaCO3 (calcite), others… SiO2 (quart)CaMg(CO3 )2 (dolomite)
Grey clinker
Tricalcium silicate, Ca3 SiO5 , C3 S, alite ~60-70 %
Dicalcium silicate, Ca2 SiO4 , C2 S, belite ~15-25 %
Tricalcium aluminate, Ca3 Al2 O6 , C3 A ~5-10 %
Tetracalcium ferroaluminate, Ca2 (Al,Fe)2 O5 , C4 AF ~10%
Minor components: ~1-4 %CaO (free lime) // MgO (periclase) Alkaline sulfates: K2 SO4 o K3 Na(SO4 )2
Precision and accuracy in quantitative phase analysisof Portland cements by using the Rietveld method
C3 S 79.98 78.33 C2 S 15.01 16.47 C3 A 5.01 5.20
Weighed(%) Weighedc (%)C3 S 60.00 58.25 C2 S 20.00 21.75 C3 A 10.00 10.29 C4 AF 10.00 9.70
Weighed(%) Weighedc (%)
C3S 62.00 60.35C2S 15.00 16.36C3A 5.00 5.16C4AF 10.00 9.73
Gypsum 4.00 4.28Basanite 4.00 4.13
Weighed(%) Weighedc (%) C3S 65.00 63.05C2S 10.00 10.87C3A 5.00 5.14C4AF 5.00 4.85
Gypsum 5.00 5.33Basanite 5.00 5.14CaCO3 5.00 5.61
Weighed(%) Weighedc (%)
Weighedc “corrected” values have been obtained by using synchrotron X-ray patterns of binary mixtures of the give phase plus standard-Al2 O3
Gray cement (6 phases) Gray cement (7 phases)
Gray clinker (4 phases)White clinker (3 phases)
C3S 79.98 78.33 79.53(5) 78.3(1) 79.0(1)C2S 15.01 16.47 15.10(13) 17.3(4) 16.2(4)C3A 5.01 5.20 5.37(6) 4.4(1) 4.8(1)
Weighed(%) Weighedc (%) SXRPD(%) LXRPD1 (%) LXRPD2 (%)
Weighed(%) Weighedc (%) SXRPD(%) LXRPD1 (%) LXRPD2 (%)
C3S 60.00 58.25 60.25(8) 60.5(2) 62.6(1)C2S 20.00 21.75 20.25(12) 22.8(2) 20.0(2)C3A 10.00 10.29 10.04(7) 8.5(1) 9.4(1)C4AF 10.00 9.70 9.46(7) 8.2(2) 8.0(2)
C3S 62.00 60.35 61.67(7) 61.1(2) 60.9(2)C2S 15.00 16.36 15.16(10) 17.7(5) 17.2(5)C3A 5.00 5.16 5.53(5) 5.1(1) 5.3(1)C4AF 10.00 9.73 9.45(6) 7.6(1) 8.0(1)
Gypsum 4.00 4.28 4.29(6) 3.9(1) 4.1(2)Basanite 4.00 4.13 3.90(6) 4.6(2) 4.5(2)
Weighed(%) Weighedc (%) SXRPD(%) LXRPD1 (%) LXRPD2 (%)
I (a
.u.)
2/º
I (a
.u.)
I (a
.u.) (c)
C3S
C3S
C3S
C3S
C3S
C2S
C3S
C2S
C3A C
4A
FC
4A
F
C3A
CaC
O3
C3S
C4A
F
C3A
C3A
(b)
(a)
(b)
(c)
CaS
O4
2H
2OC
aSO
CaS
O44 2
H2H
22OO
CaS
O4
½H
2O
I (a
.u.)
2/º
I (a
.u.)
I (a
.u.) (c)
C3S
C3S
C3S
C3S
C3S
C2S
C3S
C2S
C3A C
4A
FC
4A
F
C3A
CaC
O3
C3S
C4A
F
C3A
C3A
(b)
(a)
(b)
(c)
CaS
O4
2H
2OC
aSO
CaS
O44 2
H2H
22OO
CaS
O4
½H
2O
I (a
.u.)
2/º
I (a
.u.)
I (a
.u.) (c) C3S
C3S
C3S
C3S
C2S
C3S
C2S C
3A
C4A
F
C3A
CaC
O3
C3S
C4A
F
(b)
(a)
(b)
(c)
CaS
O4
2H2O
CaS
OC
aSO
442H2
H22OO
CaS
O4
½H
2O
I (a
.u.)
2/º
I (a
.u.)
I (a
.u.) (c) C3S
C3S
C3S
C3S
C2S
C3S
C2S C
3A
C4A
F
C3A
CaC
O3
C3S
C4A
F
(b)
(a)
(b)
(c)
CaS
O4
2H2O
CaS
OC
aSO
442H2
H22OO
CaS
O4
½H
2O
Sync
hrot
ron
pow
der
patt
ern
Lab
orat
ory
(CuK
1,
2) p
owde
r pa
tter
n
De la Torre &
Aranda, “Accuracy in Rietveld quantitative phase analysis of Portland cements”
Journal of Applied Crystallography, 2003, 36, pp 1169-1176
Very high precision with SXRPD.Good accuracy with SXRPD
Higher errors with LXRPDof the order of 2% for alite.
Relative errors for low-content phases are high (10-20%)(absolute error may be 0.5% for phases at 5% concentrations)
C3S 65.00 63.05 64.06(6) 63.82(6) 62.7(2) 62.2(2)C2S 10.00 10.87 9.66(11) 9.69(11) 11.5(3) 10.8(3)C3A 5.00 5.14 5.36(5) 5.51(4) 5.1(2) 5.2(1)C4AF 5.00 4.85 4.76(5) 4.88(5) 4.4(2) 5.1(2)
Gypsum 5.00 5.33 5.49(7) 5.55(7) 4.9(1) 4.9(2)Basanite 5.00 5.14 4.96(6) 4.85(6) 5.5(2) 5.6(2)CaCO3 5.00 5.61 5.71(6) 5.70(6) 5.9(1) 6.2(2)
Weighed(%) Weighedc(%) SXRPD1(%) SXRPD2(%) LXRPD1(%) LXRPD2(%)
C3S 65.00 63.05 64.06(6) 63.82(6) 62.7(2) 62.2(2)C2S 10.00 10.87 9.66(11) 9.69(11) 11.5(3) 10.8(3)C3A 5.00 5.14 5.36(5) 5.51(4) 5.1(2) 5.2(1)C4AF 5.00 4.85 4.76(5) 4.88(5) 4.4(2) 5.1(2)
Gypsum 5.00 5.33 5.49(7) 5.55(7) 4.9(1) 4.9(2)Basanite 5.00 5.14 4.96(6) 4.85(6) 5.5(2) 5.6(2)CaCO3 5.00 5.61 5.71(6) 5.70(6) 5.9(1) 6.2(2)
Weighed(%) Weighedc(%) SXRPD1(%) SXRPD2(%) LXRPD1(%) LXRPD2(%)
C3S 65.00 63.05 64.06(6) 63.82(6) 62.7(2) 62.2(2)C2S 10.00 10.87 9.66(11) 9.69(11) 11.5(3) 10.8(3)C3A 5.00 5.14 5.36(5) 5.51(4) 5.1(2) 5.2(1)C4AF 5.00 4.85 4.76(5) 4.88(5) 4.4(2) 5.1(2)
Gypsum 5.00 5.33 5.49(7) 5.55(7) 4.9(1) 4.9(2)Basanite 5.00 5.14 4.96(6) 4.85(6) 5.5(2) 5.6(2)CaCO3 5.00 5.61 5.71(6) 5.70(6) 5.9(1) 6.2(2)
Weighed(%) Weighedc(%) SXRPD1(%) SXRPD2(%) LXRPD1(%) LXRPD2(%)
# 3 commercial samples were also studied:(i) white Portland clinker, (ii) grey Portland clinker (iii) a type-I grey Portland cement
Just a brief summary for artificial mixture #2
Outline: QPA of cementsOutline: QPA of cements
1.
Introduction: the uses of powder diffraction
3.
Analytical method validation
7.
Conclusions
4. Polymorph determination
2.
Introduction: synchrotron radiation
5. Portland clinkers and cements
6. In-situ study of belite clinkering
C3 S Alite: 7 polymorphs with temperature
620ºC 920ºC 980ºC 990ºC 1060ºC 1070ºCT1 T2 T3 M1 M2 M3 R
Parámetros de la celda unidad Polimorfo Grupo
espacial Z a (Å) b (Å) c (Å) (º) (º) (º)
V/Z (Å3) T (ºC)/ Estabilizador
T1 1P a 18 11.670 14.240 13.720 105.5 94.3 90.0 121.7 -/-
T2 1P b 18 11.742 14.279 13.773 105.129 94.415 89.889 123.5 682/- T3 1P c 18 11.6389 14.1716 13.6434 104.982 94.622 90.107 120.346 -/0.53%MgO + 0.9%Al2O3 M1
Pcd 18 9.295 7.0792 12.221 90.0 116.08 90.0 120.4 -/Al+Fe+Mg+S M3 Cme 36 33.108 7.0355 18.521 90.0 94.137 90.0 119.15 -/1.24%MgO +0.45%Al2O3 R R3mf 9 7.135 7.135 25.586 90.0 90.0 120.0 125.3 1200/Ca2.98Si0.98Al0.04O5
(a) Golovastikov y col., 1975; (b) Peterson y col., 2004; (c) De la Torre y col. 2008; (d) De Noirfontaine y col., 2006; (e) De la Torre y col., 2002; (f) Nishi y Takéuchi, 1984.
C3 S Alite
Monoclínico M3M3
T3
T1
C2 S belite
5 polymorphs on heating
'
L '
H1425 ºC1160 ºC
780-860 ºC
690 ºC<50
0 ºC
'
L '
H1425 ºC1160 ºC
780-860 ºC
690 ºC<50
0 ºC
'
L '
H1425 ºC1160 ºC
780-860 ºC
690 ºC<50
0 ºC
Parámetros de la celda unidad Polimorfo Grupo espacial z
a / Å b / Å c / Å / ºV / Å3 Ref. bibl.
P63/mmc 2 5.420 5.420 7.027 90.0 178.8 (a) 'H Pnma 4 6.87 5.601 9.556 90.0 347.5 (b) 'L Pna21 12 20.527 9.496 5.590 90.0 1089.6 (b) P21/n 4 5.512 6.758 9.314 94.6 345.8 (a) Pbnm 4 5.081 11.224 6.778 90.0 386.5 (c)
(a) Mumme y col., 1995; (b) Mumme y col., 1996; (c) Udagawa y col., 1980.
-C2 S
-C2 S
C3 A aluminate has 4 pseudo-polymorphsParámetros de la celda unidad Na2O / % Polimorfo Grupo
espacial Z a / Å b / Å c / Å / º
V / Å3 Ref. bibl.
0-1.0 CI 3Pa 8 15.263 - - 90.0 3555.7 (a)
1.0-2.4 CII P213 8 15.248 - - 90.0 3545.2 (b)
3.7-4.6 O Pbca 4 10.879 10.845 15.106 90.0 1782.2 (b)
4.6-5.7 M P21/a 4 10.877 10.854 15.135 90.1 1786.8 (b)
(a) Mondal y Jeffery, 1975; (b) Takeuchi y col., 1980.
Foreign ions C3 A in commercial clinkers
(a) C3 A Cubic-I
(b) C3 A Cubic-II
(c) C3 A orthorhombic
(d) C3 A monoclinic
Very high alkaline contents
C3 A
C4 AF
It is not present in white clinkers/cements
Solid solution: Ca2 Alx Fe2-x O5
0<x<0.60 P cmn
0.60<x<1.33 I bm2 (in OPC, the Fe/Al ratio, x=1)
other possible phases: C2 F-C6 AF2 -C4 AF-C6 A2 F-”C2 A”
Parámetros de la celda unidad Grupo espacial Z a / Å b / Å c / Å
V / Å3 x Ref. bibl. Pcmn 4 5.559 14.771 5.429 445.8 0.0 (a) Ibm2 4 5.584 14.600 5.374 438.1 1.0 (b)
(a) Colville, 1970; (b) Colville y Géller, 1971.
0
50
100
150
200
250
11.5 16.5 21.5 26.5 31.5 36.5
fe00fe50fe100
0
50
100
150
200
250
11.5 16.5 21.5 26.5 31.5 36.5
fe00fe50fe100
C4 AF
Fe/Al ratio fixed(x=1) but the distribution Td / Ohsites changes
Fe/Al ratio change
I (u
.a.)
C3S
C3S
C3A
C2S C2S
C3S
C3S
C3S
2/º
I (u
.a.)
Arc
anit
a
CaC
O3
Arc
anit
a
C3A
C3A
C3A
Arc
anit
a
2/º
I (u
.a.)
C3S
C3S
C2S C2S
C3S
C3S
C3S
C3S
2/º
I (u
.a.)
C3S
C3S
C3A
C2S C2S
C3S
C3S
C3S
2/º
I (u
.a.)
C3S
C3S
C3A
C2S C2S
C3S
C3S
C3S
2/º
I (u
.a.)
C3S
C3S
C3A
C2S C2S
C3S
C3S
C3S
2/º
I (u
.a.)
Arc
anit
a
CaC
O3
Arc
anit
a
C3A
C3A
C3A
Arc
anit
a
2/º
I (u
.a.)
Arc
anit
a
CaC
O3
Arc
anit
a
C3A
C3A
C3A
Arc
anit
a
2/º
I (u
.a.)
Arc
anit
a
CaC
O3
Arc
anit
a
C3A
C3A
C3A
Arc
anit
a
2/º
I (u
.a.)
C3S
C3S
C2S C2S
C3S
C3S
C3S
C3S
2/º
I (u
.a.)
C3S
C3S
C2S C2S
C3S
C3S
C3S
C3S
2/º
I (u
.a.)
C3S
C3S
C2S C2S
C3S
C3S
C3S
C3S
2/º
White clinker
C3 S C2 S C3 A
Selective dissolutionAluminate enriched fraction
Selective dissolutionSilicate enriched fraction
Grey Portland clinker
C3S
C3S
C3S
C3S
C3A
C2S C
4A
F
K2SO
4
C4A
F
C2S
C3S
Clinker F6Provided sampleD5000 data
C4A
FC
3S
C3S
C3S
C3S
C3S
C3A
C2S C
4A
F
K2SO
4
C4A
F
C2S
C3S
Clinker F6Provided sampleD5000 data
C4A
FC
3S
C4A
F
C4A
F
C4A
FC3A
Clinker F6Aluminates fraction
Salic
ylic
C3A
C4A
F
C4A
F
C4A
F
C4A
FC3A
Clinker F6Aluminates fraction
Salic
ylic
C3A
C4A
F
C3S
C3S
C3S
C3S
C2S C
2S
C3SClinker F6
Silicates fraction
C3S
C3S
C3S
C3S
C3S
C3S
C2S C
2S
C3SClinker F6
Silicates fraction
C3S
C3S
Selective dissolution
Aluminate rich fraction
Selective dissolutionSilicate rich fraction
Preliminary study
C3 S C2 S, C4 AF C3 A
Selective dissolution of belite
clinkersPolymorph determination: Silicate enriched residue
Silicate residue
β-C
2Sβ-C
2S
β-C
2S
β-C
2S
β-C
2S
β-C
2S
C3S
C3S
C3S
C3S
α’H-C
2S
α’H-C
2S
C3S
α’H-C
2S
B_ref
α’H-C
2S C3S
β-C
2S
C3A
C4A
F
C3S C
3S
C3S
β-C
2S
β-C
2S
α’H-C
2S
C3S
β-C
2S
β-C
2S
α’H-C
2Sβ-
C2S
β-C
2S
Silicate residue
β-C
2Sβ-C
2S
β-C
2S
β-C
2S
β-C
2S
β-C
2S
C3S
C3S
C3S
C3S
α’H-C
2S
α’H-C
2S
C3S
α’H-C
2S
B_ref
α’H-C
2S C3S
β-C
2S
C3A
C4A
F
C3S C
3S
C3S
β-C
2S
β-C
2S
α’H-C
2S
C3S
β-C
2S
β-C
2S
α’H-C
2S
B_ref
α’H-C
2S C3S
β-C
2S
C3A
C4A
F
C3S C
3S
C3S
β-C
2S
β-C
2S
α’H-C
2S
C3S
β-C
2S
β-C
2S
α’H-C
2Sβ-
C2S
β-C
2S
B_1.5Na
C3S
C3S
C3S
C3S
C3S
α-C
2S
α-C
2S
β-C
2S
C3A
C4A
F
α’H-C
2Sβ-
C2S
C3S Silicate
residue
C3S
C3S
C3S C
3S
β-C
2S
β-C
2S
α-C
2S
α’H-C
2Sα-
C2S
α’H-C
2S
B_1.5Na
C3S
C3S
C3S
C3S
C3S
α-C
2S
α-C
2S
β-C
2S
C3A
C4A
F
α’H-C
2Sβ-
C2S
C3S Silicate
residue
C3S
C3S
C3S C
3S
β-C
2S
β-C
2S
α-C
2S
α’H-C
2Sα-
C2S
α’H-C
2S
Polymorph determination: aluminate enriched residue
B_1.5Na
C3S
C3S
C3S
C3S
C3S
α-C
2S
α-C
2S
β-C
2S
C3A
C4A
F
α’H-C
2Sβ-
C2S
B_1.5Na
C3S
C3S
C3S
C3S
C3S
α-C
2S
α-C
2S
β-C
2S
C3A
C4A
F
α’H-C
2Sβ-
C2S
C3A
ort
C3A
ort
C3A
ort
C4A
F C4A
FC
4AF
C4A
F
C3A
ort
Aluminate residue
C3A
ort
C3A
ort
C3A
ort
C4A
F C4A
FC
4AF
C4A
F
C3A
ort
Aluminate residue
B_ref
α’H-C
2S C3S
β-C
2S
C3A
C4A
F
C3S C
3S
C3S
β-C
2S
β-C
2S
α’H-C
2S
C3S
β-C
2S
β-C
2S
α’H-C
2S
B_ref
α’H-C
2S C3S
β-C
2S
C3A
C4A
F
C3S C
3S
C3S
β-C
2S
β-C
2S
α’H-C
2S
C3S
β-C
2S
β-C
2S
α’H-C
2S
C3A
cub
C3A
cub
C4A
F
C4A
F
C4A
F
C4A
F
C3A
cub
C3A
cub
C3A
cub
C4A
F
C3A
cub
C4A
F
Aluminateresidue
C3A
cub
C3A
cub
C4A
F
C4A
F
C4A
F
C4A
F
C3A
cub
C3A
cub
C3A
cub
C4A
F
C3A
cub
C4A
F
Aluminateresidue
Selective dissolution of belite
clinkers
Morsli
et al. Quantitative Phase Analysis of Laboratory-Active Belite
Clinkers bySynchrotron Powder Diffraction
Journal American Ceramic Society, 2007, 90, 3205-3212
C3 S
C3 S
C3 S C
3 S
C3 SC2 S
C2 S
C2 S
C2 S
C2 S
C3 A
C4 A
F
C4 A
FC
3 S
NK
SN
KS
NK
SN
KS
C8.5 9 9.5 10 2º 10.5
I (a.
u.)
Synchrotron powder diff. data Synchrotron powder diff. data =0.44 =0.44 ÅÅ
Polymorph determination:
C3
S, monoclinic, C m
C2
S, monoclinic, P21
/n
C4
AF, orthorhombic, Ibm2
C3
A, cubic, Pa-3 (no orth.)
Aftitalite, NaK3
(SO4
)2
, trigonal P -3m1
C, cubic, F m-3m
De la Torre et al., “Full Phase Analysis of Portland Clinker by Penetrating Synchrotron Powder Diffraction”
Analytical Chemistry, 2001, 73, pp 151-1560
Outline: QPA of cementsOutline: QPA of cements
1.
Introduction: the uses of powder diffraction
3.
Analytical method validation
7.
Conclusions
4. Polymorph determination
2.
Introduction: synchrotron radiation
5. Portland clinkers and cements
6. In-situ study of belite clinkering
Grey clinker
2/ºI
(u.a
.)
C3S
C3S
C3S C
3S
C3S
C3A
C2S C4A
F
aph
tita
lite
C4A
F
C2S
C3S
2/º
CaO
free
Free lime
I (u
.a.)
C3S
C3S
C3S C3S
C3S
C3A
C2S C
4AF
aph
tita
lite
C4A
F
C2S
C3S
CaO
free
3-4 hours
Grey clinker
I (u
.a.)
I (u
.a.)
I (u
.a.)
C3S
C3S
C3A
C2S C2S
C3S
C3S
C3S
C3S
C2S C2S
C3S
C3S
C3S
C3S
2/º
C4A
FC
4AF
C3S
C3S
C3A
C2S C2S
C3S C3S
C3S
C4A
FC
4AF
C3A
C4A
FC
4AF
(a)
(b)
(c)
*Cement # 1
Cement # 2
Cement #3 *
*
phases Cement_1
Cement_2
Cement_3
C3 S 73.7(1) 69.8(2) 73.4(3)
C2 S 8.1(3) 10.2(5) 12.5(7)
C4 AF 5.5(2) 12.4(3) 11.9(4)
C3 A 12.3(1) 4.9(2) 1.3(3)
Aphita. 0.5(1) 2.7(2) -
CaO - - 1.0(1)
I (u
.a.)
2/º
Portland cement
I (u
.a.)
2/º
gyps
um
C3S
C4A
F
Bas
san
ite
Dehydration processes in
cement mill(s)
Set up regulator
I (u
.a.)
2/ºI
(u.a
.)
2/º
C3S
C3S
C3S
C3S C
3S
C3A
C2S C
4AF
C3S
CaC
O3
CaC
O3
Additions
Other components
Portland cement
Phase CEM-1 CEM-2
Ca3 SiO5 (C3 S) 62.4 ± 0.5 65.5 ± 0.5
Ca2 SiO4 (C2 S) 8.5 ± 0.5 9.1 ± 0.5
Ca3 Al2 O6 (C3 A) 5.3 ± 0.2 5.8 ± 0.2
Ca2 AlFeO5 (C4 AF) 5.7 ± 0.3 6.2 ± 0.3
CaSO4 ·1/2H2 O (basanite) 3.8 ± 0.2 3.8 ± 0.2
CaSO4 (anhidrite) 1.3 ± 0.1 1.1 ± 0.2
SiO2 (quartz) 0.8 ± 0.1 0.3 ± 0.1*
CaCO3 (calcite) 10.8 ± 0.3 7.3 ± 0.2
CaMg(CO3 )2 (dolomite) 0.3 ± 0.2* 1.0 ± 0.2
ZnO (zincite) 1.1 ± 0.1 --
C3S
C3S
C3S
C3S
C3S
C3S
C4A
FC
3A
calc
ita
ZnO
ZnO
basa
nita
C2S
C3S
C3S
C3S
C3S
C3S
C3S
C4A
FC
3A
calc
ita
ZnO
ZnO
basa
nita
C2S
Alternative fuel study
Environmental applications(particles in suspension)
Care during sample collection
I (u
.a.)
2/º
C3S
kilnCalcite
quarry
(fingerprint/DNA)
C3S-Alita 62 %
C2S-Belita 13,2 % C4AF-Brow nmillerita 11,1 %
C3A-Aluminato tricálcico cúb. 4,8 %
Calcita 2,9 %Basanita 2,5 %Arcanita 1,8 %Yeso 1,2 %Cuarzo 0,7 %
C3S-Alita 62 %
C2S-Belita 13,2 % C4AF-Brow nmillerita 11,1 %
C3A-Aluminato tricálcico cúb. 4,8 %
Calcita 2,9 %Basanita 2,5 %Arcanita 1,8 %Yeso 1,2 %Cuarzo 0,7 %
On-line analyses
4 minutes !10-65 º/2
Outline: QPA of cementsOutline: QPA of cements
1.
Introduction: the uses of powder diffraction
3.
Analytical method validation
7.
Conclusions
4. Polymorph determination
2.
Introduction: synchrotron radiation
5. Portland clinkers and cements
6. In-situ study of belite clinkering
6. IN-SITU X-ray synchrotron study
Clinkerization process for an ordinary Portland Clinker
700-900ºC Decarbonation (CO2 )
900-1300ºC free lime, Al & Fe rich phases and silicates
1300-1450ºC liquid phase + silicates
Quenching Phase stabilisation + subcooled liquid
CO 2
CaCO 3
-Cuarzo
Arcill a
-cuarzo
CaOAlitaC 3 S
BelitaC 2 S
Fe 2 O 3
C 12 A 7C 4 AF líquido C 4 AF
C 12 A 7
140012001000 1000800600 T (ºC)
Pro
porc
ión
de C
ompu
esto
s
CO 2
CaCO 3
-Cuarzo
Arcill a
-cuarzo
CaOAlitaC 3 S
BelitaC 2 S
Fe 2 O 3
C 12 A 7C 4 AF líquido C 4 AF
C 12 A 7
140012001000 1000800600
CO 2
CaCO 3
-Quartz
Clays
-cuarzo
CaOAlitaC 3 S
BelitaC 2 S
Fe 2 O 3
C 12 A 7C 4 AF liquid C 4 AF
C 3 A
140012001000 1100800600 RT
Por
tions
by
wei
ght
C3
AC4
AF
C2
S
C3
S
Temperature (ºC) cooling
Why an in-situ study?Clinkerization process for belite clinkers is not well known
Polymorphic transformations at high temperature
Liquid appearance temperature(s)
Influence of minor elements in these reactions
5 ºC/min
1000 ºC1 h
Thermal pre-treatmentfor decarbonation
Selected compositions
1.00.50.5Bel_10S05K05N
1.0-1.0Bel_10S10K
-0.50.5Bel_05K05N
-1.5-Bel_15N
--1.0Bel_10K
---B_ref
SO3/%Na2O/%K2O/%sample
1.00.50.5Bel_10S05K05Na
1.0-1.0Bel_10S10K
-0.50.5Bel_05K05Na
-1.5-Bel_15Na
--1.0Bel_10K
---B_ref
SO3/%Na2O/%K2O/%sample
1.00.50.5Bel_10S05K05N
1.0-1.0Bel_10S10K
-0.50.5Bel_05K05N
-1.5-Bel_15N
--1.0Bel_10K
---B_ref
SO3/%Na2O/%K2O/%sample
1.00.50.5Bel_10S05K05Na
1.0-1.0Bel_10S10K
-0.50.5Bel_05K05Na
-1.5-Bel_15Na
--1.0Bel_10K
---B_ref
SO3/%Na2O/%K2O/%sample
Thermo-diffractometric
data collection
Pt capillaryØ=0.6
mm
Metallic sample holderMgO
refractory
capillary
Refractory ceramic adhesive
Raw mix inside
Data collection
ESRF (Grenoble)ID31 diffractometer=0.3007 ÅDebye Scherrer configurationCapillaries were spunAngular range 2.5-30o (in 2) 15 minutes per run3 runs for a single pattern
Real temperature was checked by Pt peak positions
Samples were heated from 900 to 1450ºC
Halogens lamps
Ceramic holder
0
10
20
30
40
50
60
70
80
wt%
900 1000 1100 1200 1300 1400
T / ºC
0
10
20
30
40
50
60
70
80
wt%
900 1000 1100 1200 1300 1400
T / ºC
Reference belite
clinker (B_ref) on heating
1240ºC
Free lime (CaO
) 9.6(2)wt%
(1) Primary formation of C4
AF ( )
Free lime (CaO
) 4.2(1)wt%(3) Formation of C3
A ( )(4) Crystal size growth of C4
AF ( )
1055ºC
C
CaOCaO
3C S
AFC4AF
-C2S
’H-C2S ’L-C2S
C A3
Liquid phase
C
CaOCaO
3C S
AFC4AF
-C2S
’H-C2S ’L-C2S
C A3
Liquid phase
0
10
20
30
40
50
60
70
80
wt%
900 1000 1100 1200 1300 1400
T / ºC
0
10
20
30
40
50
60
70
80
wt%
900 1000 1100 1200 1300 1400
T / ºC
1350ºC
(7)
’H
-C2
S -C2
S( )
C3
S ( )
1300ºC
C
CaOCaO
3C S
AFC4AF
-C2S
’H-C2S ’L-C2S
C A3
Liquid phase
C
CaOCaO
3C S
AFC4AF
-C2S
’H-C2S ’L-C2S
C A3
Liquid phase
B_ref on heating (continuing) (5) Melting
of
C3
A ( ) & C4
AF ( )(6)
’H
-C2
S( ) + CaO
C3
S ( )
Free lime (CaO
) 0.0wt%
Liquid phase ( )
Liquid
phase
(B_ref) on
heating
Nominal
compositionC4AF/% C3A/%
16 81180ºC 17.7(3) 6.2(2)
Melting
Formation
Formation/sinterization
6.30 6.35 6.40 6.45 6.50
2/º
920 ºC
1055 ºC
1180 ºC
1300 ºCCC44
AFAF
CC33
AA
Active belite clinker0.5% K2
O, 0.5% Na2
O
& 1.0% SO3
Effects of minor elements, Na, K
& S, on heating
Active belite clinker1.5% Na2
O
C3
A cubic
Na2
O stabilizesC3
A orthorhombic
1138 ºC
1140 ºC
Active belite clinker 1.0% K2
O
(B_10K) on cooling
10.0--6.5(3)3.5(1)9.5(2)10.3(2)60.2(1)--1055 ºC10.5--6.2(3)3.3(2)9.4(2)--70.6(1)--1175 ºC11.1--5.6(3)3.3(2)9.3(2)--70.7(2)--1238 ºC20.0------7.6(2)----72.4(1)1310 ºC20.0----7.1(2)----72.9(1)1308 ºC20.0------7.3(2)----72.7(1)1440 ºC--4.6(1)14.0(2)6.0(2)----75.4(1)--1200 ºC
Liquid phaseCaOC4AFC3AC3S'L-C2S'H-C2S-C2SB_1.0K
10.0--6.5(3)3.5(1)9.5(2)10.3(2)60.2(1)--1055 ºC10.5--6.2(3)3.3(2)9.4(2)--70.6(1)--1175 ºC11.1--5.6(3)3.3(2)9.3(2)--70.7(2)--1238 ºC20.0------7.6(2)----72.4(1)1310 ºC20.0----7.1(2)----72.9(1)1308 ºC20.0------7.3(2)----72.7(1)1440 ºC--4.6(1)14.0(2)6.0(2)----75.4(1)--1200 ºC
Liquid phaseCaOC4AFC3AC3S'L-C2S'H-C2S-C2SB_1.0K
5.0 5.5 6.0 6.5 7.0
1400ºC
1350ºC
1300ºC
1250ºC1200ºC
1100ºC
RT
2/º
cool
ing
5.0 5.5 6.0 6.5 7.0
1400ºC
1350ºC
1300ºC
1250ºC1200ºC
1100ºC
RT
2/º
cool
ing
Hydration of cements would need another full lecture
Both, data collection and data analysis is more complex!
Outline: QPA of cementsOutline: QPA of cements
1.
Introduction: the uses of powder diffraction
3.
Analytical method validation
7.
Conclusions
4. Polymorph determination
2.
Introduction: synchrotron radiation
5. Portland clinkers and cements
6. In-situ study of belite clinkering
Conclusions
Rietveld quantitative phase analysis gives useful information in cement chemistry.(The answer will depend on the problem)
It is useful for both:
i) Analyzing commercial samples &
ii) The study (and optimization) of laboratory cementitious materials
Acknowledgements
Many thanks to María de los Ángeles Gómez de la TorreCo-worker at Universidad de Málaga
Thanks to ESRF for providing the X-ray synchrotron beam time
Thanks to PANalytical for some specific data collection
Finally, to all of you for your attention !!
Miguel A. G. Aranda
Departamento de Química Inorgánica, Universidad de Málaga, Spain
Quantitative powder
diffraction analyses of cements
