Characterization of White Portland Cement Grinded for a Long Time by Using X-ray Powder Diffraction and 29si Nmr Spectroscopy

Cement Science and Concrete Technology, Vol.68

30

WPCXRD 29Si NMR XRD C3S C3A

5 C2S 5 10

XRD/ 29Si NMR WPC C3S

XRD NMR XRD 29Si

NMR

X 29Si NMR

*1 *2

*1060-8628 13 8 *2060-8628 13 8

X

1.

1

EMCEnergetically

Modified Cement2

3

4

Mori 5 Ca3SiO5

Ca3SiO5

Ca

Ca3SiO5

Mori 5 Ca3SiO5

Ca3SiO5 C3S

67

C3S C2S

C3AC4AF

X XRD

8

9

XRD

2

NMR

1/2

NMR

10

NMR 29Si NMR

C3S C2S


31

10, 11

XRD 29Si NMR

5100

WPC

XRD 29Si NMR

2.2. 1

WPC 3.05g/cm3 3,380cm2/g

80cc2cm

5 WPC 6.0g 4

300rpm 05102030

250rpm 100

6

WPC0WPC5WPC10WPC20

WPC30WPC100 Table 1

105 1,000

LOITable 2WPC0XRD/

2. 2

1XRD/

XRD -Al2O3

10.0wt

CuK 40kV-40mA

2 570 0.02

6.5/min 0.5

24mm

3

Siroquant V.3.0

SIETRONICS C3S

C2SC3ACaCO3

CHCaSO40.5H2O

CaSO42H2OSiO2

C3SC2S3

1

A 1 100 1

Awt

Swt

SRwt

229Si NMR

29Si NMR Bruker MSL 4009.4T

29Si Q8M8SiCH338Si8O2012.4ppm7mm

WPC 29Si

T1 5 60

10, 12 79.486MHz

3.125MHz 4kHz90

5s MASMagic Angle Spinning

512

29Si NMR Win-Nuts

Acorn NMR 20Hz

WPC 29Si NMR C3S

C2S

Rawal 10

T1

C3S 2

100100S

SSR

Table 1Grinding condition and Loss of ignitionLOIName Speedrpm Timehr LOIwt

WPC0 0 3.11

WPC5 300 5 4.92

WPC10 300 10 6.47

WPC20 300 20 7.67

WPC30 300 30 9.15

WPC100 250 100 10.52

Table 2Chemical composition and mineral composition of WPC

Chemical compositionwt Mineral compositionwt1

SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O TiO2 C3S C2S C3A Por2 Cal3 Gyp4 Bas5

21.1 5.2 0.4 69.3 0.4 2.9 0.3 0.3 0.3 9.1 34.3 5.4 3.4 1.0 2.1 3.4111.3 wt amorphous phase was determined by internal standard method for ungrinded WPC2PorPortlandite, 3CalCalcite, 4GypGypsum and 5BasBassanite


32

C3S C2S

29Si Rawal

10C3S

2 69.172.8ppmC2S 70.8ppm3

/

/

C2S

C3S

Rawal 1069ppm 73ppm C3S

6577ppm

3.3. 1XRD Fig. 1 WPC0WPC5WPC10WPC20WPC30

WPC100 XRD 570 2

Mori 5

Fig. 2 WPC0WPC10WPC30 XRD

a1020 2b2638 2Fig. 2

a10 30 WPC

C3SC2S C3A

Fig. 2b Fig. 2b 226.6

WPC0

WPC5WPC10WPC20WPC30

WPC100XRD

3. 2XRD/aC3S C2S

bC3A Fig. 3

XRD/

100wt

XRD/

WPC0 11.3wtTable 2

Fig. 3aWPC0 3. 3 29Si NMR

C-S-H Si Q1

78ppm Q283ppm

WPC0

1314Fig. 1XRD profiles from 5 to 70 2 deg.

Fig. 2XRD profiles a from 10 to 20 and b from 26 to 38 2 deg.


33

C2S 0.420.990.410.42wt/hr

C3A 0.230.220.040.05wt/hr

Fig. 4C3A C3S C2S

C3A

C3S C3A 05

C2S

510

C2S C3S

15

3. 329Si NMR WPC0 a 29Si NMR b

C3S C2S

c

Fig. 5 29Si NMR

70.8ppm C3S Fig. 5a

b C3S C2S

29Si NMR

Fig. 5

c

Fig. 6 WPC5WPC10WPC20WPC30

WPC100 29Si NMR

WPC WPC0

3. 429Si NMR

appmbHzc Fig. 7

69.172.8ppm C3S-hC3S-l 2

RIs 2Is

Is

X

1015

WPC 14

WPC0

C3S

C2S C3A

Fig. 3ab250rpm100

60wt

C3SC2S C3A

XRD/

C3SC2S C3A

C3S C2S C3A

Fig. 4 C3S C2S C3A

XRD/

C3SC2S C3A

WPC100

Fig. 4

C3S 05510102020

30 1.11.070.480.36wt/hr

Fig. 4Rate of amorphization of C3S, C2S and C3A

Fig. 3Weight fraction of a C3S, C2S, and amorphous phase and b C3A from XRD/Rietveld analysis


34

C3S-h C3S-l

Fig. 2bC2S

77.94.4Hz

Fig. 7b

c3. 529Si NMR 29Si NMR

RIss

Iss

sC3S-hC2S C3S-l

Fig. 7a C3S-h 69.10.36ppmC2S70.70.14ppmC3S-l 72.80.28ppm

Fig. 5 29Si NMR spectra of anhydrous white Portland cement WPC0a observed spectrum, b 29Si signals from unhydrated C3S and C2S, and c simulated spectrum

Fig. 7 Relation between grinding time with a chemical shift, ppm, b full width at half maximum Hz, and c relative intensity of C3S and C2S optimized in least-squares fitting to the

29Si NMR spectra

Fig. 6 29Si NMR spectra of WPC5, WPC10, WPC20, WPC30, and WPC100 and 29Si signals from unreacted C3S and C2S


35

XRD/ C3S 39.1wt

C2S 34.3wtTable 1NMR

XRD/ WPC

Fig. 8 29Si NMR C3S C2S

C3S

C2S 3. 6XRD 29Si NMR Fig. 9 XRD/ 29Si NMR

C3S C2S C2S

XRD/ 29Si NMR

C3S

WPC100 XRD 20.4wt

NMR 59.3wtC3S

38.9wt

XRD/

C3S C2S

C3S C2S C2S

XRD NMR

Fig. 9

C3S

29Si

NMR

WPC 2

13

iC3S

38.9wtiiWPC0

11.3wtiii C3S

C3S

C2S

WPC0 29Si 29Si NMR C3S

SiO2 3

1012

Taylor 16 C3S

C2S Ca2.9Si0.95Mg0.06Al0.04 Fe0.03P0.01Na0.01O5Ca1.94Si0.9Al0.07K0.03Fe0.02Mg0.02 P0.01Na0.01O3.93 C3S

C3S-h C3S-l

mxRAx Mx 3

mxx wt

RAxx

CASiO2SiO2 wt

MSiO2SiO2 60.08g/mol

Mxx g/mol

xC3S C2S

RAC3S

RAC2S

AC3SAC2SC3S C2S

29Si NMR WPC0 C3SC2S

0.470.53 34

37.631.9wt

CASiO2MSiO2

AC3SAC3SAC2S

AC2SAC3SAC2S

Fig. 8 Relation between grinding time and weight fraction of C3S circle and C2Ssquare quantified by 29Si NMR

Fig. 9 Comparison with weight fraction of C3S circle and C2S square quantified by XRD and by 29Si NMR


36

C2S

C3S C2S

69.1ppm 72.8ppm Fig. 7b

4.XRD/ 29Si NMR

WPC

1

2 C3S C2S

3 69.1 72.8ppm

4 XRD/ 29Si NMR C2S

C3S

5 29Si NMR XRD

C3S C2S C3S

XRD/ 29Si NMR R20.81

1

p. 1361971

2 EMC Cementhttp://www.emccement.com

3 K. Johansson et al.Kinetics of the hydration reac-

tions in the cement paste with mechanochemically

modified cement 29Si magic-angle-spinning NMR

study, Cem. Concr. Res., 29, pp. 1575-15811999

4 L. Elfgren et al.High performance concretes with

energetically modified cementEMC, Technical

Paper Series prepared by EMC Cement BV, pp. 1-

102013

5 K. Mori et al.Structural and hydration properties

of amorphous tricalcium silicate, Cem. Concr. Res.,

36, pp. 2033-20382006

6 F. Nishi et al.Tricalcium silicate Ca3OSiO4

the monoclinic superstructure, Z. Kristallogr., 172,

pp. 297-3141985

7

86pp. 195-2021978

8 H.M. RietveldA profile refinement method for

nuclear and magnetic structures, J. Appl. Cryst., 2,

pp. 65-711969

9 A. G. De la Torre et al.Rietveld quantitative

amorphous content analysis, J. Appl. Cryst., 34,

pp. 196-2022001

10 A. Rawal et al.Molecular silicate and aluminate

C3S C3S C2S

4 29Si NMR C3S

WcC3SNMRC3SWaC3SWaC2S 4

WcC3S29Si NMR C3S

wt

NMRC3S29Si NMR C3S

wt

WaC3S C3S wt

WaC2S C2S wt

WaC3SXRDt,C3SXRD0,C3S

WaC2SXRDt,C2SXRD0,C2S

XRDt,C3SXRD WPC t C3S

wt

t05102030100

XRD0,C3SXRD WPC0 C3S

wt

XRDt,C2SXRD WPC t C2S

wt

XRD0,C2SXRD WPC0 C2S

wt

Fig. 10 XRD C3S 4

NMR C3S

Fig. 10 XRD NMR C3S

70.8ppm

Fig. 10 Comparison with weight fraction of crystalline C3S by XRD and

29Si NMR


37

cement clinker, Cem. Concr. Res., 9, pp. 757-763

1979

14 X

68

CD-ROM2014

15

23pp. 156-1591969

16 H.F.W. TaylorModif ication of the Bogue

calculation, Adv. Cem. Res., 2, pp. 73-771989

species in anhydrous and hydrated cements, J. Am.

Chem. Soc., 132, pp. 7321-73372010

11 J. Skibsted and H. J. JakobsenQuantification of

calcium silicate phases in Portland cements by 29Si

MAS NMR spectroscopy, J. Chem. Soc. Faraday

Trans., 91, pp. 4423-44301995

12 I. F. Saez del Bosque et al.Effect of temperature

on C-S-H gel nanostructure in white cement,

Mater. Struct., DOI 10.1617/s11527-013-0156-8

2013

13 I. MakiMechanism of glass formation in Portland

Tomotaka AWAMURA*1 and Toyoharu NAWA*2

ABSTRACTLong time grinding by planetary ball mill was carried out to get white Portland cementWPCsamples including high weight fraction of amorphous phases. It was confirmed, from X-ray powder diffractionXRD/Rietveld analysis using an internal standard that major components in WPC, alite, belite and aluminateC3S, C2S and C3A in cement chemistry notation, partly changed to the amorphous state. Approximately 60wt of the sample converted to amorphous state after grinding for 100h at 250rpm. In addition, the rate of amorphization of C3S and C3A was the highest in 05h grinding, while the amorphization rate of C2S was the highest in 510h. Moreover, it is observed from 29Si MAS NMR analysis that the full width at half maximum heightFWHMof the C3S signals got broader by grinding, while FWHM of the C2S signal was almost constant. Furthermore, C3S and C2S weight fraction were calculated using molar percentages obtained after deconvolution of the 29Si NMR spectra and the total amount of SiO2 determined with X-ray fluorescence analysis. There was different correlation between amount of C3S from XRD/Rietveld analysis and that from NMR. We carried out the modification to the amount of C3S from NMR analysis using amount of amorphous C3S and amorphous C2S determined from XRD. Then the quantity of crystalline C3S from the two different methods showed positive correlation of R

20.81. It was suggested that the 29Si signal of 70.8ppm belongs to crystalline C2S and that mechano-chemically modified calcium silicate minerals showed wide range of their in 29Si NMR spectra.

KEY WORDSWhite Portland cement, X-ray powder diffraction, 29Si MAS NMR, Amorphization, Alite, Belite

CHARACTERIZATION OF WHITE PORTLAND CEMENT GRINDED FOR A LONG TIME BY USING X-RAY POWDER

DIFFRACTION AND 29Si NMR SPECTROSCOPY

*1 HOKKAIDO UNIVERSITY, Graduate School of EngineeringNorth13-West8, Kita-ku, Sapporo-shi, Hokkaido 060-8628, Japan

*2 HOKKAIDO UNIVERSITY, Faculty of EngineeringNorth13-West8, Kita-ku, Sapporo-shi, Hokkaido 060-8628, Japan

Documents

Characterization of White Portland Cement Grinded for a Long Time by Using X-ray Powder Diffraction and 29si Nmr Spectroscopy