X-Ray Powder Diffraction and Cement Hydration:

Transmission versus reflection geometry

A. Cuesta, G. Alvarez-Pinazo, M. García-Maté, I. Santacruz, L. León-reina, M.A.G. Aranda, A.G. De la Torre

a_cuesta@uma.es

is a very complex process in which crystalline phases are dissolving in water, supersaturating it in corresponding ions to promote hydrated crystalline and amorphous phases
precipitation. Great efforts are being made to develop analytical tools to accurately quantify these processes and X-ray Powder Diffraction (XRPD) combined with Rietveld methodology is a
suitable/powerful tool to quantify these complex mixtures. However, some problems/drawbacks should be overcome to fully apply it to cement pastes characterization in order to get good/accurate phase
analyses [1].
The study presented here concerns on of laboratory belite calcium sulfoaluminate (BCSA) cements by XRPD. These cements are receiving increasing attention for
their environment benefits as their manufacture releases less CO2 into atmosphere than ordinary Portland cements (OPCs). Anhydrous BCSA cements contain as main phases C2S, C4A3S, C4AF,
gypsum and sometimes non-negligible amorphous and crystalline non-quantified (ACn) phases [2]. Moreover, hydrated pastes contain different amounts of ettringite [C6AS3H32], strätlingite [C2ASH8],
AFm phases or katoite [C3ASH4] as hydrated products, jointly with remaining anhydrous unreacted phases.
presents some difficulties, i. e. some of them exhibit clearly preferred orientation (for instance ettringite) or their peaks are broad due to poor crystallization
stage or structural disorder.
Sample averaging is a concern as there are up to nine crystalline phases in hydrated pastes. Working on transmission mode enhances particle statistics as much volume of sample is bathed by x-rays.
Working with high energetic Mo-radiation in transmission mode will be also discussed.

X-Rays
Transmission geometry: Flat sample Influence of amount of sample (thickness) on resolution and RQPA
WSlits
D
X-Rays 0.16 SK64G36
WSlits Larger
0.14
thicknesses yield Attenuation factor 5.5 2.8 1.7
Pd poorer resolution measured
Wmask 0.12
t (wider peaks) C4A3S /wt% 63.9(1) 64.5(1) 64.5(1)
0.10
Gypsum /wt% 33.3(2) 32.7(2) 32.5(2)
Wmask
C2AS /wt% 1.3(1) 1.1(1) 1.4(1)
D 0.08 RF-Gyp / % 8.1 7.9 7.4
Virr= 1/3 · ·Pd·(R2 + r2 + R·r)
where R=D/2 and r=Wmask/2
P.O.-Gyp 1.220(7) 1.230(7) 1.220(6)
0.06 Attenuation factors
Example CuK :
Example CuK :: 5.5
=167 cm- 1 Example MoK :: 0.04
Pd 12.7 m (63%of attenuation) =167 cm-1 2.8
2 =40º =18.1 cm-1 Virr= ·R2·t
Pd 58 m (99% of attenuation) (Attenuation factor=2.77*; t= 75 m where R=D/2 1.7
Packing=80% (Attenuation factor=2.77*;
0.02 Actual added value for gypsum =34.0 wt%
is corresponding to 63%) t= 704 m Deviations of quantities of gypsum are due to
*Wslits=6.214 mm Packing=80% is corresponding to 63%) 0.00 the misfitting of C4A3S, as crystal structure
Wmask=12.8 mm Virrad 1.8 mm3 (63%) Wslits=0.7 mm Virrad 5.9 mm3 Packing=80% 10 20 30 40 50 60 70 description used is poor.
Virrad 8.3 mm3 (99%) Wmask= 10 mm Wslits=0.6 mm
*This value is angle depended. Wmask= 20 mm Virrad 221 mm3 º(2 )
*This factor has been experimentally calculated

Stopping hydration
Measured mixtures Name procedure
Hydration procedure Radiation: CuK 1
B0 B2 64.1 wt% C4A3S + 35.9 wt% Gypsum SK64G36 Reflection-Cu:, 3h, 5-70º
H’-C2S - 50.2(2) 75 wt% CSA + 25% Gypsum CS10-25 w/c=0.55 Step size: 0.017
- C2S 46.5(2) - Stored 95% RH
90 wt% B0 + 10 wt% Gypsum C10B0 Radiation: CuK 1,2
-C2S 2.3(1) -
C4A3S ort 12.5(4) - 95 wt% B2 + 5 wt% Gypsum C5B2 Transmission-Cu: 3h, 5-70º
Step size: 0.013
C4A3S cub 15.0(4) 34.1(1) 90 wt% B2 + 10 wt% Gypsum C10B2 Samples Stopping time
C4AF 15.3(2) 14.2(3) SK64G36 anhydrous
CS10-25 anhydrous
Radiation: MoK 1,2 (K 2
C2AS 4.9(1)
This gypsum also contains CaSO4 and SrSO4 5wt% C10B0 28d 1º Washing with acetone-fast. stripped mathematically)
C3A 2.6(1) Ground samples =
2º Washing with acetone-slow. Transmission-Mo: 2h, 3-31º
C5B2 28d fine and homogeneous.
CT - 1.5(1) 3º Washing with ether-slow. Step size: 0.017
C10B2 28d
RWP/% 3.7 4.3

CS10-25 For accuracy studying on RQPA C10B2

Actual added value for gypsum =23.8 wt%
Hydrated samples
Reflection (R) - Cu
Deviations of amount of gypsum are due to the misfitting of C4A3S, as crystal structure
description used is poor. C5B2 C10B0 C10B2
wt% R-Cu T-Cu T-Mo R-Cu T-Cu T-Mo R-Cu T-Cu T-Mo
/wt% R- Cu T-Cu T-Mo
´-C2S 31.1(2) 24.7(3) 33.8(4) - - - 32.7(2) 23.7(3) 34.8(4)
C4A3S 48.7(5) 51.2(1) 51.5(2)
-C2S - - - 17.9(2) 18.1(2) 18.8(3) - - -
Gypsum 31.0(2) 28.0(2) 26.8(3) Working on transmission with Mo -C2S - - - 2.4(1) 2.0(1) 2.3(1) - - -
-C2S 10.4(3) 11.3(5) 11.3(3) the RQPA obtained matches the
C2AS 1.8(1) 1.6(1) 1.8(2) 3.7(1) 2.8(1) 3.7(1) 1.6(1) 1.0(1) 1.8(1)
CT 6.5(2) 7.1(1) 7.1(2) expected value (i.e: gypsum=23.8
wt%) better than the results CT 0.8(1) 0.5(1) 1.0(1) - - - 0.9(1) 0.6(1) 1.1(1)
MgO 1.5(1) 1.0(1) 1.8(1)
obtained on reflection geometry. Ett 20.2(2) 26.1(2) 15.8(3) 23.0(2) 23.4(2) 22.0(3) 35.1(2) 40.4(2) 28.7(3)
Akerm 1.2(1) 1.3(2) 1.3(1)
Strat 26.7(6) 21.7(5) 23.5(5) 40.0(5) 41.6(4) 40.7(1) 14.0(9) 12.4(4) 11.3(5)
C4AF 0.7(1) - 0.6(1)
Kat 18.9(3) 25.0(3) 23.2(4) 11.6(2) 12.0(3) 12.3(4) 15.7(5) 21.8(4) 22.3(6)
RF-Gyp /% 4.9 5.4 2.9
Gib 0.6(1) 0.3(1) 0.8(1) - - - - - -
P.O.-Gyp 0.733(2) 1.290(7) 1.080(8) Higher volume enhances Transmission (T) - Cu
particle statistics. AFm - - - 1.3(2) - - - - -
Consequently, RF values are RF-Ett / % 3.6 3.0 3.5 3.2 3.6 3.5 2.6 2.6 3.8
lower with Mo-K . RF-Strat / % 1.2 1.5 1.8 1.4 1.5 1.8 1.6 1.5 2.1
Working on reflection-Cu, P.O.
has to be corrected P.O.-Ett 1.12(2) 1.14(1) 1.10(3) 1.14(2) 1.15(2) 1.06(2) 1.17(1) 1.17(1) 1.13(2)

Gypsum is a P.O.-Strat 1.00(-) 1.00(-) 1.00(-) 1.00(-) 1.00(-) 1.00(-) 1.00(1) 1.00(1) 1.00(-)
Working on transmission-Cu, P.O. is not
laminar compound
minimized and has to be corrected
Preferred
(sample preparation induces P.O)
orientation (P.O.) Stratlingite is a laminar phase.
Ettringite crystallizes as needle
along (020) Working on transmission-Mo, P.O. is However in this complex
shape particles. Working on
minimized as higher volume decreases the mixture (with more than seven
reflection or transmission P.O.
P.O. induced by sample preparation phases) this phase does not
has to be corrected along (001).
present preferred orientation.

CS10-25 Reflection (R) - Cu CS10-25 Transmission (T) - Mo Transmission (T) - Mo

Most reliable results are those obtained with
transmission-Mo mode as higher volume of
P.O. sample are analyzed ( better sample
P.O.
averaging)
Reflection-Cu results match properly those of
transmission- Mo.
Transmission-Cu mode date are of low-
resolution as K 1,2 is used. Rietveld QPA
obtained using these data yield to less
precise results.

This study has revealed that Rietveld QPA obtained using reflection-Cu mode (available at most XRD facilities) are
satisfactory. [1] Aranda M.A.G., De la Torre A.G., León-Reina L.
Some samples with different ages of hydration have been analyzed with XRPD (reflection and transmission mode) and , 74, 169, 2012.
Rietveld methodology, and quantitative phase analyses have been compared and we have established a protocol to [2] Álvarez-Pinazo G., Cuesta A., García-Maté M.,
obtained proper fits of XRPD patterns.
Santacruz I., Losilla E.R., De la Torre A.G., León-Reina L.,
As irradiated volumen is an important parameter to obtain accurate Rietveld QPA the combination of high energetic Mo
radiation on transmission geometry is strongly advisable. Aranda M.A.G., 2012, 42, 960.

Acknowledgments: We thank PANalytical B.V. for providing a Mo-Cuk equipment (Almelo, the Netherlands). We also thank the financial support by MAT2010-16213.