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Mtodo de Rietveld-Quantitativo

Intensidade Calculada de um material contendo muitas fases:


Howard e Hill, Howard e Bish.

*
y ci = y bi + s p L kp .Fkp .Fkp
(2i 2kp )Pkp .A p
p

Fator de Escala
proporcional massa
de cada fase e ao tempo

Sp

mp
Z p .M p .V p

tempo

Roberto R. de Avillez 2004

CeO2 + ZrO2
Sonia Letichevsky, Marco A. Fraga, Lucia
G. Appel e M. Isabel Pais da Silva
Coprecipitation of mixed oxides and solid
solutions from Ce(NO3)3 e (NH4)2Ce(NO3)6
XDR: CuK, 40kV, 30mA, graphite
monochromator, Bragg-Brentano
geometry.

Roberto R. de Avillez 2004

CeO2+ZrO2+MgO* (internal standard)

Roberto R. de Avillez 2004

CeO2*+ZrO2+MgO*

Roberto R. de Avillez 2004

CeO2*(cs)+ZrO2+MgO*

Roberto R. de Avillez 2004

CeO2*(cs)+ZrO2*(cs)+MgO*

Roberto R. de Avillez 2004

CeO2*(cs)+ZrO2*(cs)+MgO*

Roberto R. de Avillez 2004

Results: CeO2+ZrO2
Phase

Lattice
Parameter
(Angstron)

%Mass

Crystallite
size (nm)

CeO2

5,412

74,5

15,1

ZrO2

5,259

25,5

6,1

Absorption=
499,9

Rexp= 28,46

Rwp= 31,30

GOF= 1,10

Roberto R. de Avillez 2004

(Ce,Zr)O2 + MgO

Roberto R. de Avillez 2004

Resultados do Ajuste: (Ce,Zr)O2


Fase

Parmetro
da rede
cristalina
(Angstron)

%Massa

Tamanho do
Cristalito
(nm)

(Ce,Zr)O2

5,349

100

6,8

ZrO2

Absoro=
498,7

Rexp= 27,59

Rwp= 30,49

GOF= 1,10

Ce sublattice occupation: 0,74 Ce + 0,26 Zr


Roberto R. de Avillez 2004

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Quantitative analysis of amorphous


phase
Rafael Cardoso, Maria Cecilia de S. Nobrega
Porcelains for dental prostheses
XDR: CuK, 40 kV, 30 mA, graphite
monochromator
Roberto R. de Avillez 2004

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Rietveld Method-Internal standard


Sample with amorphous + crystalline materials
Initial mass of the sample: ms
Internal standard mass, mp

wc =

wa + wc = 1
ms + m p = m

m p Sc (ZMV )c

ms S p (ZMV ) p
Roberto R. de Avillez 2004

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Dental porcelain

Roberto R. de Avillez 2004

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Quantitative analysis of leucite and


amorphous
Phase

Mass, g

%mass,
determined
by XDR

Al2O3

0,0263

59,05

Leucite

40,95

%mass, in the
original sample

26,3

K2O.Al2O3.4SiO2

Original
sample
(amorphous)

0,1445

Roberto R. de Avillez 2004

(73,7)

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Lattice parameter changes of


Zeolites
Bojan Marinkovic, Paula M. Jardim, Fernando C.
Rizzo Assuno, Alvaro Saavedra, Lam Y. Lau,
Michael Knapp e Carsten Bhtz.
The influence of the temperature on the crystal
lattice of ZSM-5 zeolite.
DRX: Luz Sincrotron, HAZYLAB, = 0.9088 A,
Debye-Scherrer.
Roberto R. de Avillez 2004

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Zeolite Structure

Roberto R. de Avillez 2004

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ZSM-5 Crystalline Structure


Estrutura cristalina da ZSM-5

a
c
b
Roberto R. de Avillez 2004

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ZSM-5 Results

Roberto R. de Avillez 2004

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ZSM-5: XRD as a function of the


temperature
50000

ZSM-5

30000

20000

40 C
o
80 C
o
120 C
o
160 C
o
320 C

Counts

40000

5
4

20000

6
10000
4.4

4.6

4.8

5.0

5.2

5.4

5.6

10000
13.0

13.2

13.4

13.6

13.8

14.0

14.2

14.4

14.6

14.8

Roberto R. de Avillez 2004

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Unit cell volume as a function of


temperature
Negative thermal expansion
5400
5380

aps o resfriamento

volume da clula unitria (A )

Counts

ZSM-5

40 C
o
80 C
o
120 C
o
160 C
o
320 C

5360
5340
5320
5300
5280
5260
0

200

400

600

800

1000

Temperatura ( C)
Roberto R. de Avillez 2004

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15.0

Crystallite size distribution


Bojan Marinkovic, Alvaro Saavedra,
Fernando C. Rizzo Assuno
Crystallite size distribution in a mixture of
Bohemite, prepared by CENPESPETROBRAS.
Materials Research-Revista Ibero Americana de
Materiais, So Carlos, 4, 1-6 (2001).

XDR: CuK, graphite monochromator,


Bragg-Brentano geometry
Roberto R. de Avillez 2004

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Warren-Averbach method
Advantages
Separation of the contributions from the
crystallite size and deformation (distortion)
Determination of the crystallite size
distribution

Difficulties
Decomposition of the peak in Fourier series
Requires the deconvolution of the equipment
and sample effects
Requires a standard sample

Roberto R. de Avillez 2004

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Results for the Crystallite Size


Distributions
Warren-Averbach
Balzar
Enzo et al.
Sample Dv Ds <2>1/2 Dv Ds <2>1/2 Dv Ds <2>1/2
80 53 43 0.0011 61 63 0.0165
61 51 0.0018
200 143 103 0.0005 242 125 0.0017 245 125 0.0002
Mixture 106 64 0.0008 129 64 0.0035 128 78 0.0005
Mixture is a 50 w% of each nominal sample.
Crystalite sizes are in ngstrons.
<2>1/2 is calculated at Dv/2.

Roberto R. de Avillez 2004

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Geometria associada ao feixe de


Raios-X

Colimador de Raios-X

Roberto R. de Avillez 2004

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