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Cristalografa de las fases en las muestras

LaB6: Grupo espacial Pm3m (221), coordenadas fraccionarias de los tomos


tomo
La
B

Sitio
1a
6f

x
0
0.199

y
0
0.5

Z
0
0.5

Parmetros de red: a = 4.16 A

CeO2: Grupo espacial Fm3m (225), coordenadas fraccionarias de los tomos


tomo
Ce
O

Sitio
4a
8c

x
0
0.25

y
0
0.25

z
0
0.25

Parmetros de red:a = 5.41 A

Rutilo: Grupo espacial P42/mnm(136), coordenadas fraccionarias de los tomos


tomo
Sitio
x
y
z
Ti
2a
0
0
0
O
4f
u
u
0
u = 0.3046
Parmetros de red:a = 4.59556 A, c = 2.95996

Factor de Lorentz y polarizacin de los rayos X


La intensidad asociada a cada pico del patron de difraccin depende del tiempo
que los rayos X pasan en los planos de difraccin (Factor de Lorentz) y de la
polarizacin parcial del haz de rayos X en el monocromador y en la muestra.
Esto aspectos influyen en la intensidad de los picos de difraccin, la cual depende
del ngulo de difraccin de acuerdo a la siguiente relacin:
ILP = I * (1+Cos2(M)*Cos2(2))/(Sin2()Cos())
Mes el ngulo de difraccin en el monocromador is the scattering angle in the
monochromator
Para una ptica sin monocromadorM = 0 grados.
Par una radiacin totalmente polarizada (Radiacin de Sinchrotrn) M = 90
grados.
Los valores de M para los monocromadores ms comunes empleados con
radiacin de cobre se presentan a continuacin:
Germanio : 27.3 grados
Grafito : 26.4 grados
Quarzo : 26.6 grados

Las siguientes notas se dejaron en el Idioma Ingls, tal como


se encontraron en la literatura.
Polarisation, P
It is fairly obvious that the direction of polarization of an X-ray photon can change as a
result of scattering/diffraction. In fact there are two extreme cases to consider; when the
change is maximal or when there is no change, depending on whether the initial
polarization is or is not in the plane containing the pre- and post-scattered X-rays:

In the first case, the component of polarization resolved along the new (diffracted) direction
is reduced by the cosine of the scattering angle (conventionally 2) and so the reduction in
intensity would be by cos2 2 (since intensity is proportional to the square of the
amplitude). In the second case, the component of polarization is clearly unaffected, and
therefore unchanged, by the diffraction process so we would say, mathematically speaking,
that the reduction factor is "1". These two extreme cases can in principle be realised by
diffractometers on synchrotron sources due to the special polarised nature of the X-rays
produced by synchrotron sources (see earlier section on Instrumentation: Synchrotron
Sources and Methods). There is a third case, a mixture of the above two, which occurs with
laboratory diffractometers since laboratory X-ray sources produce unpolarised X-rays, that
is X-rays polarised equally in all possible directions; here the reduction factor will be the
mean of the two previous extreme cases. We could summarise these three situations as
follows:
Case (1): Polarisation in plane of scattering,

P = cos2 2

Case (2): Polarisation perpendicular to plane of scattering,

P=1

Case (3): Unpolarised X-rays,


P = (1 + cos2 2 )/2
These three cases are shown graphically below (in red, dark blue, and magenta,
respectively):

There are some obvious conclusions from all of this:

Case (1): You would not use this arrangement out of choice since this has the worst
reductions in intensity; in fact it is disastrously reduced to zero at 2 = 90; i.e. you
would not be able to see any diffraction at all at this angle! However this case is
used in a negative sense in spectroscopy measurements where diffraction effects are
unwanted; for this reason spectroscopy measurements are often deliberately
performed at 2 = 90 to remove the diffraction component.

Case (2): This is obviously the best case of all since there is no loss of intensity
anywhere due to polarisation. For this reason synchrotron diffractometers are
usually set in this configuration.

Case (3): The reduction centred at 90 is unavoidable with laboratory


diffractometers and obviously must be corrected for.

Now lets look at our case problem again, the 200 and 111 reflections in NaCl. To calculate
the effect of polarisation here we need some additional information: that the measurements
are done on a laboratory powder diffractometer using copper K X-rays. Armed with this
we will calculate the correction for the 111 case, and again for easy reference we will
structure the model answer:
(1) Working out the angles , 2 :
First we remind you how to calculate the d spacing in cubic crystals:

dhkl = a/(h2 + k2 + l2 )1/2


d111 = 5.638/(12 + 12 + 12 )1/2 = 5.638/3 = 3.255
For Copper K radiation the wavelength is about 1.54 , and so inserting into Bragg's law
gives us:
1.54 = 2 3.255 sin
sin = 0.237
= sin1(0.237) = 13.68
2 = 27.37
(2) CalculatingP111 :
For the laboratory powder diffractometer we use the formula of Case (3):
2 = 27.37
cos (2) = 0.888
cos2 (2) = 0.789
1 + cos2 (2) = 1.789
P111 = (1 + cos2 (2 ))/2 = 0.894
So polarisation produces a reduction in intensity to 89% in the case of the 111 reflection.
From the graphs, you should be able to see that it is reduced more for the 200 reflection,
due to its smaller d spacing.

Polarisation&Monochromators
An unpolarized laboratory X-ray source diffracted by monochromator crystal produces a
partially polarized X-ray beam. As for a diffracting sample, the degree of polarisation
depends upon the diffraction angle, 2M, of the monochromator. Assuming that the source,
monochromator, sample, and detector are all in the same plane, then the polarisation factor
in the presence of a monochromator is given by the expression:
P = (1 + cos2 2M cos2 2) / (1 + cos2 2M)
Given that 2M is small, the effect of the cos2 2M in this expression is small as shown in the
figure below, where the solid line is the polarisation factor without a monochromator and
the dotted curve shows the polarisation correction with 2M set to 28.44 (as for a Si<111>
and Cu K1).

The expression is correct whether the monochromator is pre or post sample. However, there
has been some debate as to whether cos2 2M or |cos 2M| should be used when the
monochromator is a perfect crystal, e.g. Si<111> (for similar reasons to the use of |F| versus
F2 for intensity given in the earlier page on dynamic versus kinematic diffraction). If a
crystal structure is refined from laboratory data collected with a monochromator and a
monochromator polarization correction is not applied, then the thermal parameters will
appear to be larger than expected so as to compensate for the lack of correction.
An alternative scenario is the case of a pre-sample monochromator on a powder diffraction
synchrotron beamline. Here the incident beam is 100% plane polarized. Assuming that the
monochromator and diffractometer all function in the vertical plane, then the polarization
remains unchanged from source to detector, so that no additional correction is required due
to the monochromator.

Lorentz Factor, L
In previous discussions we have referred to ideas such as random crystallite orientations
and the statistical likelihood of such crystallites being correctly oriented for diffraction.
Bragg's law seems to imply that diffraction only occurs when the equation is satisfied
exactly. In reality, the parameters to be fulfilled in Bragg's law (, d) will have a finite
spread so that diffraction occurs in practice over a small range of angles around the mean,
2. Translated into the language of the reciprocal lattice used earlier, one would say that the
reciprocal lattice points are not infinitesimal mathematical points of zero size, and similarly
the Ewald sphere is not a vanishingly thin shell: the difference between the two is
illustrated below:

In the left-hand "mathematical picture" a reciprocal lattice point is found to be slightly off
the Ewald sphere which is equivalent to saying that diffraction will not occur unless the
crystallite is re-oriented slightly to bring it onto the sphere; however in the "real" right-hand
picture intersection (and therefore also diffraction) still occurs in spite of this slight misorientation. Given this latter more realistic view one might next ask what is the overall
statistical probability, under the conditions pertaining to the powder diffraction experiment,
that intersection/diffraction will occur? It turns out that the answer varies according to the
experimental arrangement used. For standard powder diffraction arrangements the
relationship is:
L = c / (sin sin2)
or, alternatively,
L = c / (sin2cos)
Both expressions appear in the literature and differ only by the definition of the constant c
(since sin2 = 2sincos). The precise value of the constant, which can be set to unity, is

unimportant since, in general we only calculate the relative intensities of reflections. The
shape of the function is shown in the plot below:

It may be useful to consider the real-space processes that give rise to the Lorentz factor.
Considering the Debye-Scherrer cones of scattered radiation from a powder sample, then a
detector of finite aperture will have the potential to count more photons at low (or equally
at high) angle, and less as the scattering angle approaches 90. The amount of the DebyeScherrer cone measured is simply inversely proportional to the sine of the scattering angle
2, i.e. 1/sin2. The second term relates the probability of the crystallites having a plane in
the correct orientation for Bragg scattering, and this is inversely proportional to the sine of
the incident Bragg angle , i.e. 1/sin.
Again taking the NaCl 111 reflection, and using the value for theta already obtained in the
polarization calculation:
= 13.68
sin = 0.237
sin 2 = 0.460
sin sin 2 = 0.1087
L = 1 / (sin sin 2) = 9.20
This is a relatively large value compared to, say, values of L for 2 values nearer to 90.
You can see from the graph that the L value for the 200 reflection will be much smaller. In

addition, note that the powder patterns of materials with large dspacings are likely to have
very intense reflections at low diffraction angles due to the Lorentz factor.

Focus

Detec tor

GEOMETRY = REFLEXION
FocusW

DetW
HSlitW

Primary
C ollimator

Secondary
C ollimator

SSlitW
Sample

HSlitR
R

T
SSlitR

R
MonR

VSlitR

FocusH

VSlitW
Primary
Collimator

SamplD
SamplW

SamplH

Secondary
Collimator

GEOMETRY = TRANSMISSION

a [mm]
PC oll = b/a = tan()

b [mm]

SampleD

DetH

MonH

Muestra:LaB6
Fecha: 03/09/2012

Medicin: Difraccin de rayos X

ptica del difractmetro empleado:


Equipo
Geometra
Configuracin
Dimetro de la geometra
nodo del tubo de rayos X
Haz del tubo de rayos X
Voltaje y corriente en el tubo de rayos X
Monocromador
Colimador Soller en el haz incidente
Apertura de divergencia
Apertura de salida
Cortador de fondo en el haz primario
muestra
Apertura del haz difractado
Colimador Soller en el haz difractado
Filtro de Kbeta en el haz difractado
Absorbedor
Monocromador secundario
Apertura en el detector
Detector
(Lynxeye)
rea activa mxima del detector
Ventana activa del detector

Bruker D8 Advance
BraggBrentano
Theta-Theta
435 mm
Cobre
Foco fino 0.04 x 12 mm
40kV, 35 mA
Ninguno
1.5 grados
0.5 grados
Ninguna
0.5 mm arriba de la

Condiciones de medicin:
Intervalos (en grados) de medicin en 2 theta
Modo de barrido del gonimetro
Incremento en 2 theta
Tiempo de medicin (en segundos) por punto
Tiempo total de la medicin por muestra
Intensidad
Rotacin de la muestra
Portamuestras
Archivos de datos generado con DIFFRAC Plus

8.0 mm
2.5 grados
Nquel 0.5 %
Ninguno
Ninguno
0.075 mm
Tira mltiple de Si
14mm x 16mm
3.43 grados
2-60 grados
Barrido contnuo
0.0195 grados
72 segundos
21:00 minutos
Cuentas
No
Vidrio
LaB6-4hrs-06-05-09.raw