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CURSO DE DIFRACCIÓN DE RAYOS-X DE

MUESTRAS POLICRISTALINAS

TEMA II
FUNDAMENTOS DE LA DIFRACCIÓN DE
RAYOS-X

Orientado por: José Antonio Henao Martínez

ANTECEDENTES

Wilhelm Roentgen, 1895 Max von Laue, 1912 W. L. Bragg, 1912
Descubrió los Rayos-X. Demostró el fenómeno de difracción Determinó la primera
de rayos-X en sólidos. estructura cristalina.

Fotografía tomada por Max Von Laue, Friedrich y Knipping en 1912 al
sulfato de cobre

INFORMACIÓN GENERAL CONTENIDA EN UN PATRÓN DE DIFRACCIÓN DE POLVO R. L. E. J. (2008) . Dinnebier and S. “Powder Diffraction. RSC Publishing. Billinge. Theory and Practice”.

PROPIEDADES Y FUENTES DE RADIACIÓN .

NATURALEZA Y PROPIEDADES DE LOS RAYOS-X 0. P.5Å Pecharsky. V. Springer. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”.1----------100Å Rango más comúnmente usado 0. (2003) . Y..5 . K. Zavalij.2.

(2003) . Zavalij. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. V. K.Pecharsky.. Y. P. Springer.

K. V. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”.Pecharsky. (2003) . Y. Zavalij. P.. Springer.

.

Jenkins. “Introduction to X-ray Powder Diffractometry”. . L. R and Snyder R. Inc. John Wiley & Sons.

L.Jenkins. . “Introduction to X-ray Powder Diffractometry”. Inc. R and Snyder R. John Wiley & Sons.

R. Billinge. J. RSC Publishing. Dinnebier and S. “Powder Diffraction. Theory and Practice”. (2008) . E.Diagrama de niveles de energía para el átomo de cobre neutro. L.

Transiciones electrónicas en un modelo atómico durante el proceso de desexcitación. .

.

Y. K. (2003) . Zavalij. Springer. ESPECTRO DE RAYOS-X CARACTERÍSTICO Pecharsky. P. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”.. V.

(2003) .. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. Springer. P. Y. K. Zavalij.Pecharsky. V.

“Fundamentals of Powder Diffraction and Structural Characterization of Materials”. P. Y. controlled by a magnetic field.. Both the brilliance of the beam and the coherence of the generated electromagnetic waves are exceptionally high. Springer. where beams of accelerated electrons or positrons are moving in a circular orbit. The synchrotron output power exceeds that of the conventional x-ray tube by many orders of magnitude (≈ twelve). . They are the most powerful x-ray radiation sources today. V. FUENTES DE RADIACIÓN SINCROTRÓN Synchrotron radiation sources were developed and successfully brought on line beginning in 1960’s. K. Zavalij. (2003). Pecharsky. at relativistic velocities. Tremendous energies are stored in synchrotron rings. Pp 112 and 113.

in Long Island. New York.  APS . (2003).UK.Advanced Light Source at Berkeley Lab. although its availability is restricted to the existing synchrotron sites.National Synchrotron Light Source at Brookhaven National Laboratory. in Warrington. in Berkeley. France. US. Zavalij. Springer. FUENTES DE RADIACIÓN SINCROTRÓN Thus.European Synchrotron Radiation Facility in Grenoble. P. in Campinas. Brazil. Cheshire .. synchrotron radiation finds more and more use today.Synchrotron Radiation Source at Daresbury Laboratory. Pp 112 and 113.. US  SRS . Some of the well- known sites are:  ALS . US. and others. Illinois.  ESRF . V.  LNLS – Laboratorio Nacional de Luz Sincrotrón. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. K. California.  NSLS . Pecharsky. Y. . in Argone.Advanced Photon Source at Argonne National Laboratory.

(2008). Dinnebier and S. RSC Publishing. P 26 . Third generation machines have many straight sections and are optimised for the exploitation of wiggler and undulator insertion devices as X ray sources. L. Theory and Practice”. R.Schematic illustration of a synchrotron storage ring. Billinge. “Powder Diffraction. J. E.

ESQUEMA DE UN SINCROTRÓN Fuente: Wikipedia .

.

European Synchrotron Radiation Facility (ESRF). Grenoble, Fraance.

Fuente: Wikipedia

OTHER TYPES OF RADIATION

Other types of radiation that are commonly used in diffraction analysis are neutrons and
electrons. Neutrons are usually produced in nuclear reactors; they have variable
energy and therefore, a white spectrum.

The main differences when compared to x-rays are as follows:
i) neutrons are scattered by nuclei, which are much smaller than electron clouds,
and the scattering occurs on points;
ii) scattering factors of elements remain constant over the whole range of Bragg
angles;
iii) scattering functions are not proportional to the atomic number and they are
different for different isotopes of the same chemical element.

Furthermore, since neutrons have spins, they interact with the unpaired electron spins
(magnetic moments) and thus neutron diffraction data are commonly used to determine
ordered magnetic structures.

Pecharsky, V. K., Zavalij, P. Y. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. Springer. (2003). Pp
113-115.

OTHER TYPES OF RADIATION…

In addition to the direct imaging of crystal lattices (e.g. in a high- resolution transmission
electron microscope-HRTEM), electrons may be used in diffraction analysis. Despite
the ease of the production of electrons by heating a filament in vacuum, electron
diffraction is not as broadly used as x-ray diffraction:

First, the experiments should be conducted in high vacuum, which is inconvenient
and may result in the decomposition of some materials.

Second, electrons strongly interact with materials. The latter requires the use of the
dynamical theory of diffraction, thus making structure determination and refinement quite
complex.

Finally, the complexity and the cost of a high-resolution electron microscope
usually considerably exceed those of a high-resolution powder diffractometer.

Pecharsky, V. K., Zavalij, P. Y. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. Springer. (2003). Pp
115.

Pecharsky.rl. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. In the US. Vol. . (2003). K.ac.. NY (1992).sns.gov/) is scheduled for completion in 2006.. Ed. Oxford University Press.uk/). 2One of the brightest operational pulsed neutron sources (ISIS) is located in the UK (http://www. J. Cowley. V. Springer. Zavalij. the construction of the spallation source at the Oak Ridge National Laboratory (http://www.isis. Pp 113-115.1Electron diffraction techniques. P. 1. Y. M.

the x-ray beam should be monochromatized by reducing the intensity of white radiation and by eliminating the undesirable characteristic wavelengths from the x-ray spectrum.  Using diffraction from a crystal monochromator (any source. including neutrons). The most common methods utilized in the instrumental monochromatization of x-ray beams are as follows:  Using a ß-filter (conventional x-ray sources only).  Pulse height selection using a proportional counter (x-rays).  Energy resolution using a solid-state detector (x-rays). . Monochromatization In addition to collimation. leaving only a single usable wavelength.

Springer. which can be defined using the following differential equation integrating where µ is the proportionality coefficient expressed in the units of the inverse distance. when an x-ray beam travels the infinitesimal distance. Absorption of X-ray and ß-filters When x-rays penetrate into the matter. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. dx.. Thus. Y. (2003) . Zavalij. usually in cm-’. its intensity is reduced by the infinitesimal fraction dI/I (Figure left). Pecharsky. K. This coefficient is also known as the linear absorption coefficient of a material. they are partially transmitted and partially absorbed. V. P.

Springer.Pecharsky. Zavalij. (2003) . P. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. V. Y.. K.

Fuente: Bruker .

“Fundamentals of Powder Diffraction and Structural Characterization of Materials”. EL MONOCROMADOR Pecharsky. P. (2003) . V. Springer. Zavalij. K.. Y.

one or two spatial dimensions. but as more open systems they are prone to detecting parasitic scatter from the air or sample environment. X-RAY DETECTORS X-Ray detectors may be classified as point. Both linear and area detectors are types of Position Sensitive Detector (PSD). whereas linear or area detectors can be fixed. Point detectors must be scanned to measure the diffraction pattern. Point detectors are easily compatible with post-sample optical elements. linear or area. Linear and area detectors allow the data to be acquired much faster. depending on whether they record the diffraction pattern in zero. .

Detectores modernos de DRX de Bruker AXS Capabilidades VÅNTEC-2000 HI-STAR VÅNTEC-1 LynxEye Sol-X Scinti Dimensiones .

.POINT DETECTORS SCINTILLATION COUNTER Los detectores de rayos X operan en modo de contadores de fotones: cada cuanto de radiación absorbido por el transductor produce un pulso de corriente registrándose la potencia del haz digitalmente en cuentas por unidad de tiempo.

LINEAR DETECTORS LINEAR POSITION SENSITIVE DETECTOR (PSD) LynxEye BRUKER AXS .

ya que la detección de cada una de las imágenes que se recogen (con varios cientos o miles de reflexiones) se hace en un tiempo mínimo. el desarrollo de la tecnología electrónica ha dado lugar a la aparición de los denominados detectores de área. ahorrando con ello tiempo en el experimento. que permiten la detección de muchos haces de difracción simultáneamente. del orden de los segundos. los detectores CCD (Charge Coupled Device) y los detectores Image Plate. . DETECTORES DE ÁREA Como alternativa a los detectores "puntuales". Esta tecnología es de especial utilidad para el caso de las proteínas y en general de cualquier material que pueda deteriorarse durante su exposición a los rayos X. Actualmente se tienen en el comercio dos tipos de detectores de área.

DETECTORES CCD
(Charge Coupled Device)

Goniómetro de geometría Kappa Detalle del montaje de un
con detector tipo CCD. goniómetro con geometría Kappa.
(Imagen tomada de Bruker-Nonius)

Image Plate Scanner
Especialmente utilizado en la Cristalografía de proteínas.

Image Plate Scanner. Detalle de un detector del tipo Image Plate
(Imagen tomada de Mar Research) Scanner

High Resolution XRPD on NIST
1976, Scintillation counter
1100

1000 D8 ADVANCE
900 1,100 counts  35 kV, 50 mA
 0.3° divergence
800
 2.5° Soller
Intensity [counts]

700  0.3° anti-scatter
600
 2.5° Soller
 0.5% Ni-filter
500
 0.1 mm receiving slit
400  0.006° step size
300
 1 sec/step

200

100

0

25 30 40 50 60 70

2-Theta [deg]

BRUKER AXS

50 mA 140000  0. detector lineal LynxEyeTM D8 ADVANCE 150000  35 kV.000 counts  2.3° anti-scatter  2.006° step size 60000  1 sec/step 50000 40000 30000 20000 10000 0 25 30 40 50 60 70 2-Theta [deg] BRUKER AXS .5° Soller 120000 110000  0.3° divergence 130000 150.5% Ni-filter 80000  3° opening 70000  0.Alta Resolución de DRX con NIST 1976.5° Soller Intensity [counts] 100000 90000  0.

.

de una proteína recogida en un Image Plate Scanner. o de varios segundos en una instalación de sincrotrón) el cristal gira aproximadamente 0.Aspecto de una de las imágenes de difracción. Durante la exposición de cada una de estas imágenes (unos 10 minutos con un generador de ánodo rotatorio. del tipo oscilación.5º y la lectura de la imagen dura unos 30 segundos. .

L. “Powder Diffraction. RSC Publishing. P 42 . Theory and Practice”. Dinnebier and S. E. J. (2008). PORTA MUESTRAS (SAMPLE HOLDERS) R. Billinge.

RSC Publishing.CAPILARES DE VÍDRIO PARA GEOMETRÍA DE TRANSMISIÓN R. E. P 42 . L. Theory and Practice”. Dinnebier and S. “Powder Diffraction. Billinge. (2008). J.

Esquema del Difractómetro de Debye Scherrer equipado con monocromador y muestra montada en un capilar. Billinge. P 37 . E. RSC Publishing. L. Dinnebier and S. (2008). R. “Powder Diffraction. J. Theory and Practice”.

V. Springer. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. P. K. (2003).. Zavalij. P 138 . Y. Dispersión elástica de un haz incidente Pecharsky.

V. Y. Zavalij. P. K. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. Dispersión por electrones Pecharsky. Springer.. P 141 . (2003).

. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. P 143 . (2003). P. Dispersión por un átomo Pecharsky. K. Zavalij. Springer. Y. V.

LEY DE BRAGG .

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. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. Y. P 150 . (2003). Springer. Zavalij. P. V. K. Red recíproca y Esfera de Ewald Pecharsky.

Y. (2003). Zavalij. V. P. P 151 .. Springer.Pecharsky. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. K.

Springer.Pecharsky. P 151 . V. Zavalij.. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. (2003). K. Y. P.

V. Y.Pecharsky.. K. Springer. P. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. (2003). P 152 . Zavalij.

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. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. V. P 153 . Zavalij. Y. Springer. EL ORIGEN DEL PATRÓN DE DIFRACCIÓN DE POLVO Pecharsky. K. P. (2003).

“Fundamentals of Powder Diffraction and Structural Characterization of Materials”. V. K. (2003).Pecharsky. Springer.. P. Y. Zavalij. P 155 .

V. K. Picos de Bragg observados a partir de cobre policristalino usando radiación de cobre K1 Pecharsky. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. Zavalij.. (2003). Y. P. Springer. P 154 .

“Fundamentals of Powder Diffraction and Structural Characterization of Materials”. K. Y. P. P 157 .. Springer. Zavalij. V.Pecharsky. (2003).

P 156 . Springer. (2003). P. Patrón de difracción de Rayos-X del LaB6 registrado con un detector de Área CCD. K. Pecharsky. Zavalij. Y.. V. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”.

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P 15 . E. L.Imágenes tomadas en un detector bidimensional. “Powder Diffraction. R. Theory and Practice”. (2008). J. Dinnebier and S. Billinge. RSC Publishing.

. (2003). Springer. Y. Pecharsky. Zavalij. K. P 161 . P. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. V. Entendimiento del Patrón de Difracción de Polvo.

los cuales definen esencialmente la estructura de cada patrón de polvo. .Además de la influencia ejercida por los parámetros instrumentales. las dimensiones de la celda unidad y la estructura atómica (el contenido de la celda unidad y la distribución de los átomos en la celda unidad). hay dos clases de parámetros cristalográficos (estructurales). Ellos son.

el espacio- dhkl.Bajo estas consideraciones. un patrón de difracción de polvo se puede construir (o simular) de la siguiente manera: 1. . es decir. Las posiciones de los picos de Bragg son establecidas a partir de la Ley de Bragg como una función de la longitud de onda y las distancias interplanares.

 Tipo de átomos. .  Movimientos térmicos y  Parámetros poblacionales  Parámetros geométricos (factores instrumentales como las propiedades de la radiación. La intensidad del máximo de difracción es función de la periodicidad de los centros de dispersión (celdas unidad) y por lo tanto. tipo de geometría del foco. propiedades del detector. las intensidades pueden ser calculadas para picos de Bragg individuales a partir de un modelo estructural. El modelo estructural. requiere el conocimiento de las  Coordenadas de los átomos en la celda unidad.2. rendijas y la geometría del monocromador) y  Parámetros atómicos (tamaño y distribución de los granos y microestructura. entre otros) relevantes.

La forma de cada pico puede ser modelada usando características del especímen y del instrumento. .3.La forma de los picos de Bragg es usualmente representada por una función similar a una campana llamada función de forma del pico. La función de onda del pico depende de la estructura del cristal y es la convolución de varias funciones individuales. establecidas por los parámetros instrumentales y en alguna extensión por las propiedades del especímen.

V. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. Zavalij. K. Springer. P 163 . (2003)..Pecharsky. P. Y.

APARIENCIA DEL PERFIL DE DIFRACCIÓN Posición de los picos de Bragg Intensidad Forma de los picos de Bragg Pecharsky. V. Y. Springer. Zavalij.. P. K. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. (2003). P 162 .

Posición de los picos como una función de las dimensiones de la celda unidad Pecharsky. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. V. Zavalij. Springer. (2003). Y. K. P. P 165 ..

V. Springer..Pecharsky. K. P. (2003). “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. Zavalij. P 165 . Y.

“Fundamentals of Powder Diffraction and Structural Characterization of Materials”.cos2β . P 165 . c (1 . (2003).. V. K. P. Zavalij. Y. Red Romboédrica primitiva (R) a = b = c y  =  =  ≠ 90° Volumen de la celda unidad V = (a x b) .cos2γ + 2 cos α cos β + 2 cos α cos γ + 2 cos β cos γ)1/2 Pecharsky. c = a. Springer. b.cos2α .

K.. P. is a sum of three non-coplanar vectors (a*. Y. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. Any reciprocal lattice vector. d*hkl. V. P 167 .Consider a reciprocal lattice as shown schematically in the next Figure. (2003). k and l are integers): Pecharsky. Zavalij. Springer. b* and c* are the unit vectors of the reciprocal lattice and h.

Springer. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. K.35 is transformed into and Eq. P. Hence. P 166 . 2. b* = 1/b and c* = 1/c. the equivalent of Eq. Zavalij.For example: in the orthorhombic crystal system α* = ß* = ɣ* = 90°. Eq.. Y. is obtained immediately because d* = 1/d. 2. In the general case (triclinic crystal system). (2003).36 is more complex Pecharsky. V. a* = 1/a.

K. These factors are often known as systematic aberrations (distortions). Zavalij. 2Θobs. various instrumental and specimen features may affect the observed positions of Bragg peaks. and they are usually assembled into a single correction parameter. P 168 . V. Other factors affecting peak positions The preview equations are exact assuming that both the powder diffractometer and the sample are ideal. so that the experimentally observed Bragg angle. Springer. (2003). Δ2Θ.. P. In reality. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. The latter is applied to the idealized Bragg angle. is given as Pecharsky. calculated from the unit cell dimensions and wavelengths. 2Θcalc. Y.

(2003). Zavalij.. K1 and K2 are constants established by the collimator. V. R is the goniometer radius. Springer.For the most commonly used Bragg-Brentano focusing geometry. Pecharsky. pl and p2. the overall correction is generally a sum of six factors: The first two parameters. these two corrections are often neglected for practical purposes. Y. Soller slits usually minimize the axial divergence and therefore. K. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. P 168 . P. account for the axial divergence of the incident beam and they can be expressed as where h is the length of the specimen parallel to the goniometer axis.

Jenkins. R. P 191 . “Introduction to x-ray powder diffractometry. Inc. R. Snyder. L.. John Willey & Sons.

(2003). Y. p3. V. K. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. P. typically used in Bragg-Brentano goniometers. The aberrations are generally insignificant and they are usually neglected in routine powder diffraction experiments. Springer. Pecharsky. is given as where α is the in-plane divergence of the x-ray beam and K3 is a constant. Zavalij.. This factor accounts for the zero curvature of flat samples. P 168 .The third parameter.

The transparency shift error is caused by the penetration of the beam into the sample and the penetration depth is a function of Bragg angle. Usually p4 is the refined parameter since µeff is rarely known (both the porosity and the density of the powder sample are usually unknown). K.g. V. and it is usually negligible for highly absorbing specimens. The transparency shift error could be substantial for low absorbing samples. (2003). “Fundamentals of Powder Diffraction and Structural Characterization of Materials”.The fourth parameter is where µeff is the effective linear absorption coefficient.e. Zavalij. Y. P. This correction is known as the transparency shift error and it may play a role when examining thick (more than 50 to 100 pm) samples. Pecharsky. i. Springer. e. P 169 .. organic compounds. compounds containing heavy chemical elements.

K. Pecharsky. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. This correction may be substantial. Zavalij. Springer. Y. (2003).. P 169 . s. V. from the goniometer axis and it is expressed as where R is the radius of the goniometer.The fifth parameter characterizes specimen displacement. P. especially when there is no good and easy way to control the exact position of the specimen surface.

P.The last parameter. The zero shift error can be easily minimized by proper alignment of the goniometer. in neutron powder diffraction. Y. Zavalij.g. (2003). should be always accounted for. therefore. P 169 . “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. p6. Pecharsky. Hence. e. in some cases.. V. zero shift is practically unavoidable and. is constant over the whole range of Bragg angles and the corresponding aberration usually arises due to improper setting(s) of zero angles for one or more diffractometer axes: detector and/or x-ray source. However. Springer. this distortion is called the zero shift error. K.

P 170 . Pecharsky. Zavalij. Springer.. P.When the powder diffractometer is well aligned and when axial divergence is small. V. usually only the specimen displacement correction (p5) is required. (2003). Y. K. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”.

Zavalij. V. K.e. The same is also needed in structure refinement using the full profile fitting approach . and the limited resolution of the instrument .. Springer. P 171 .the Rietveld method. Pecharsky. Thus. P. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. i. (2003). processing of the data by fitting peak shapes to a suitable function is required in order to obtain both the positions and intensities of individual Bragg peaks. Y. Shapes of Powder diffraction peaks All but the simplest powder diffraction patterns are composed from more or less overlapped Bragg peaks due to the intrinsic one-dimensionality of the powder diffraction technique coupled with the usually large number of "visible" reciprocal lattice points. those that have d*hkl ≤ 2/λ.

Ψ. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. Springer. P 171 . and specimen function. PSF can be represented as follows: where b is the background function. (2003). Thus. V.The observed peak shapes are best described by the so-called peak shape function (PSF). Ω. P. Λ. wavelength dispersion. Zavalij. K. which is a convolution of three different functions: instrumental broadening. Pecharsky.. Y.

(2003). Ψ The specimen function. V. Y. depends on multiple geometrical parameters: the locations and geometry of the source. Specimen function. Springer. Second effect is determined by the physical properties of the specimen: crystallite (grain) size and microstrains.Instrumental broadening. or deviations from the kinematical model. when the crystallites are small (usually smaller than ≈ 1µm) and/or they are strained. and specimen. Ψ. the resultant Bragg peak widths may increase substantially. P. Pecharsky. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”.. Zavalij. K. For example. monochromator(s). slits. P 172 . They yield a small but finite width (the so-called Darwin width: uncertainty in the d- spacing for the perfect crystals due the primary extinction) of the Bragg peaks. originates from several effects. First is dynamic scattering. Ω. Ω The instrumental function.

BRUKER .particle or grain size crystal size crystallite size domain size User´s Manual TOPAS ACADEMIC. Version 4.

Zavalij. effects of the average crystallite size (Ƭ) and microstrain (Ɛ) on Bragg peak broadening (ß. Pecharsky. the broadening effects introduced by the physical state of the specimen may be of interest in materials characterization. Y. in radians) can be described in the first approximation as follows: where k is a constant that depends on the definition of a microstrain.It is worth noting that unlike the instrumental and wavelength dispersion functions. is not the total breadth of a Bragg peak but it is an excess width. It is important to note that ß in Eqs. P 172 . which is an addition to all instrumental contributions. P. (2003).. K. Thus. The latter is usually established by measuring a standard material without microstrain and grain size effects at the same experimental conditions. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. Springer. V.

In general. Zavalij.. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. The second is a semi-empirical approach that describes instrumental and wavelength dispersion functions using empirical functions. which fit the profile without attempting to associate their parameters with physical quantities. K. Y. P 172 . Springer. In the third. V. the so-called fundamental parameters approach. three different approaches to the description of peak shapes can be used: The first employs empirical peak shape functions. Pecharsky. P. (2003). while specimen properties are modeled using realistic physical parameters. all three components of the peak shape function (PSF) are modeled using rational physical quantities.

Funciones empíricas de la forma del pico. .

Funciones empíricas de la forma del pico. Parámetro de mezcla de la función pseudo-Voigt. . Fórmula de Caglioti. es el FWHM como función de  para las funciones de Gauss. pseudo-Voigt y Pearson.VII. Es el FWHM como función de  para la funciónde Lorentz.

.

Uso de la función Pearson-VII para ajustar un dato experimental representando un único pico In the most general case the peak full width at half maximum at a specific 2Θ angle is represented as .

Springer. P. The solid line represents a least squares fit using H with U = 0.003410. V= -0. V. Y.. Zavalij. P 177 .Experimentally observed full width at half maximum of LaB6 (open circles) as a function of 2Θ. Pecharsky.004462. (2003). K. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”.001264. and W= 0.

slit and/or monochromator geometry. Numerous factors have either central or secondary roles in determining peak intensities: i) structural factors. such as properties of radiation. which have different intensities in addition to varying positions and shapes. ii) specimen factors owing to its shape and size. and iii) instrumental factors. type of focusing geometry. microstructure and other parameters of the sample. properties of the detector. which are determined by the crystal structure. grain size and distribution. Intensity of Powder Diffraction Peaks Any powder diffraction pattern is composed of multiple Bragg peaks. .

Relación entre la forma del pico de Bragg medido y la intensidad integrada. .

such as certain specimen and instrumental parameters. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. V. and after including necessary details.. (2003). earlier grouped as "geometrical" effects. P. Zavalij. K. Considering Eq. Springer. the calculated integrated intensity in powder diffraction is expressed as the following product: Scale factor Multiplicity Absorption Preferred factor multip orientation factor Lorentz Polarization Extinction Structure multiplier factor multiplier factor Pecharsky.Integrated Intensity The integrated intensity is a function of the atomic structure and it also depends on multiple factors. Y. P 187 .

This translates into scattering from multiple reciprocal lattice vectors at identical Bragg angles.. P. 001 and 00-1.Multiplicity Factor (Phkl) As we established earlier. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. Consider two points in a reciprocal lattice. Zavalij. K. Pecharsky. Y. a powder diffraction pattern is one-dimensional but the associated reciprocal lattice is three-dimensional. (2003). Thus.By examining Equation it is easy to see that in any crystal system l/d2(001) = l/d2(00-1). Springer. V. Bragg reflections from these two reciprocal lattice points will be observed at exactly the same Bragg angle. P 187 .

K. P. Y. Simple analysis of Eq. V. therefore. Springer. a function of lattice symmetry and combination of Miller indices.Multiplicity Factor (Phkl)…cont Consider the orthorhombic crystal system. (2003). indicates that the following groups of reciprocal lattice points will have identical reciprocal lattice vector lengths and thus. Pecharsky. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. are equivalent in terms of the corresponding Bragg angle: The multiplicity factor is. Zavalij.. P 187 .

The first is owing to finite size of reciprocal lattice points and finite thickness of the Ewald’s sphere. and the second is due to variable radii of the Debye rings.Lorentz (Lo) –polarization (Po) Factor The Lorentz factor takes into account two different geometrical effects and it has two components. Both components are functions of Θ. .

K = 0. When a monochromator is employed. it introduces additional polarization.Lorentz (Lo) –polarization (Po) Factor…cont The polarization factor arises from partial polarization of the electromagnetic wave after scattering. measured) or refined. and K is the fractional polarization of the beam. which is accounted as: where 2ΘM is the Bragg angle of the reflection from a monochromator (it is a constant for a fixed wavelength).e. while for a monochromatic or synchrotron radiation K should be established experimentally (i. for unpolarized and unmonochromatized characteristic x-ray radiation.5 and cos2ΘM = 1. . For neutrons K = 0.

which in the case when no monochromator is employed is given as: or assuming K = 0.Lorentz (Lo) –polarization (Po) Factor…cont The Lorentz and polarization contributions to the scattered intensity are nearly always combined together in a single Lorentz-polarization factor.5 with a crystal monochromator .

“Fundamentals of Powder Diffraction and Structural Characterization of Materials”. Y. V. (2003). Zavalij.. K. Springer. P 192 . P.Lorentz (Lo) –polarization (Po) Factor…cont Pecharsky.

“Fundamentals of Powder Diffraction and Structural Characterization of Materials”.Absorption Factor (AΘ) Absorption effects in powder diffraction are dependent on both the geometry and properties of the sample and the focussing method. P. (2003). Y. Pecharsky. Zavalij. P 193 .. K. V. Springer.

precisely the same fraction of the specimen volume should be in the reflecting position for each and every Bragg reflection. In other words. Nonetheless. In practice it can be only achieved when the number of crystallites is very large (usually in excess of 106 to 107 particles). even when the number of crystallites approaches infinity. this does not necessarily mean that their orientations will be completely random. Strictly speaking this is possible only when the specimen contains an infinite number of crystallites. .Preferred orientation (Thkl) Conventional theory of powder diffraction assumes completely random distribution of the orientations among the infinite amount of crystallites in a specimen used to produce a powder diffraction pattern.

quite often the shapes are anisotropic.Preferred orientation (Thkl)…cont The external shape of the crystallites plays an important role in achieving randomness of their orientations in addition to their number. The non-random particle orientation is called preferred orientation and it may cause considerable distortions of the scattered intensity. However. e. platelet-like or needle-like and this results in the introduction of distinctly non-random crystallite orientations due to natural preferences in packing of the anisotropic particles.g. . When the shapes of crystallites are isotropic. random distribution of their orientations is not a problem and deviations from an ideal sample are usually negligible.

In powders diffraction the extinction factor is nearly always neglected. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”. Pecharsky. which occurs within the same crystallite. V. may be noticeable in diffraction from nearly perfect and/or large mosaic crystals. Two types of extinction are generally recognized: primary. P 203 . P. and secondary. Zavalij. Springer. K. (2003).Extinction Factor (Ehkl) Extinction effects.. which are dynamical in nature. Y. which originates from multiple crystallites.

when the unit cell contains many atoms and they have different scattering ability. 2 Structure amplitude Fhkl When the unit cell contains only one atom. the resulting diffracted intensity is only a function of the scattering ability of this atom. However. the amplitude of the scattered wave is given by a complex function. which is called the structure amplitude: .

Taking into account the previous Equation. the equation of the structure amplitude can be written in the expanded form as: .

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8. 4. Así. . mientras que la reflexión (110) sería vista. 10. La primera reflexión observada en una celda unidad BCC es la (110). 12. Celda BCC (h2 + k2 + l2 = 2. 16…) Para que una reflexión de una celda unidad bcc (cúbica centrada en el cuerpo) sea observada en un patrón de difracción. 6. debe ocurrir que la suma de los índices de Miller sea un número par. esto es. 14. no se verían las reflexiones (100) y (111).

De esta manera. 8. l deben ser todos pares o todos impares. 12. 11. la reflexión (110) estaría ausente pero la reflexión (111) estaría presente. k. 16…) La condición para que sea observada una reflexión en una celda unidad FCC (cúbica centrada en las caras) es que h. . Celda FCC (h2 + k2 + l2 = 3. 4.

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(2003).. P. K. V. P 213 .Pecharsky. Y. Zavalij. Springer. “Fundamentals of Powder Diffraction and Structural Characterization of Materials”.