Sample handling
For absorptive measurements, the sample must be sufficiently thin so as not to
absorb all of incident X-RAY radiations. If a metal to be examined, a thin piece of
metallic foil can be used as solutions can be held in a cell which has transparent
windows that are constructed from a material which only contains elements with
low atomic number, often thin sheets of [polyethylene terephthalate] type of
plastic is used as windows.
WAVELENGTH DISPERSIVE DEVICES
Absorptive and fluorescent measurements should be made while using
monochromatic incident radiations. The radiations come from cell can be made
monochromatic prior to being with the detector or polychromatic radiations can be
used in combination with a detector that distinguish between radiation of different
energies. FILTERS and wavelength dispersive devices [monochromators] can be
used to make the radiations monochromatic. Filters are used for analysis are thin
metallic foils; the metal is chosen so that its K-edge at a wavelength that is either
just slightly longer or slightly shorter than the wavelength of Radiation which is
used for assay. Metallic filters can be used in either of two ways: the balanced
method uses two filters to isolate radiation of desired wavelength. The first filter
has an absorptive edge at a wavelength which is slightly shorter than wavelength at
which the measurement is to be made. K-edge sudden increase in X-ray
absorption occurring when the energy of X-ray matches the binding energy of
crystal. The second filter which has an absorptive edge at a wavelength which is
slightly less than that of absorptive of the analyte is used in edge place of first
filter. A second absorptive is made and difference between the two measurements
is proportional to concentration of analyte. The thickness of two filters must be
such that two filters absorb radiation to same extent in all regions in which both
filters absorb. The analytical technique in which measurements are made before
and after absorptive edge of an analyte is the absorptive edge method. Wavelength
greater than K-edge are transmitted while shorter wavelengths are absorbed. A
second method of radiation filtration takes advantage of differences in absorptive
coefficients of a single filter at two wavelengths. The method is used during
measurements of X-ray fluorescence or X-ray diffraction. For example, nickel
filters can be used to isolate the copper Kₐ line from the Kᵦ line during X-ray
crystallographic studies when source is an X-ray that contain a copper target. The
metals which have atomic number less than target metal should be used.
Crystal
The crystals can be used as reflective diffraction gratings. The crystal which is
used for the dispersion is analyzing crystal. A monochromator consists of an
analyzing crystal between entrance and exit slits or collimators. The
monochromator uses a flat crystal and consequently is easier to construct. The
optical system uses a curved crystal at the outer edge of a Rowland circle. The flat
reflective crystals are used more often than curved crystals. Reflective wavelength
dispersive crystals which are used for X-ray analysis obey Bragg Equation:
n=2dsinθ
where:
n is the order of diffracted radiation,
λ\lambda is the wavelength that is diffracted at angle θ relative to the
crystalline surface,
d is the spacing between adjacent crystal planes.
The factor "2" in the equation is the result of the reflected radiation successively
passing twice across the space between adjacent planes in the crystal. Incident
radiation passes between atoms in the top layer of the crystal and is reflected from
atoms in the second layer. The radiation again passes through the space between
layers and exits from the crystal.
For a particular angle of incidence and a fixed distance between layers in the
crystal, the only radiation that is reflected in phase from successive layers of
analyzing crystal corresponds to that with an integral multiple nnn of the
wavelength.
The radiative path through a monochromator utilizes a flat crystal. The radiation
strikes and is reflected from the crystal at an angle. The wavelength of radiation
which strikes the detector is altered by simultaneously rotating the crystal, the exit
collimation, and the detector relative to the incident radiation. The rotatable
platform upon which the crystal, exit collimation, and detector are mounted
ensures correct alignment.
The detector is mounted on a goniometer.
Goniometers are carefully made to permit accurate measurement of the angle at
which the incident radiation strikes the analyzing crystal. Reflection, of course,
occurs when the angle of the incident radiation equals the angle of reflection.