Mossbauer velocities

Fe which have full width 2r at 0.2 mm s . Other isotopes are less demanding, e.g., Au, for which the lines are ten times wider. Most spectrometers are equipped with electromechanical Mossbauer velocity transducers of the loudspeaker type. This technique is suitable for velocity variations ranging from less than 1 mm s full scale up to several cm s and covers the whole reach of hyperfine splitting for most of the common isotopes. Kalvius, Kankeleit, Cranshaw, and others [1-5] have been pioneers in the field, who laid foundations for the development of high-precision drives with feedback amplifiers for proper linear velocity scales with high stability and low hum. Other techniques for Doppler modulation have been developed for isotopes with extremely narrow hyperfine lines, e.g., Zn. For such isotopes, piezoelectric transducers are mostly used [6, 7], more details of which are found in Sect. 7.2.1. 

Figure 4.16. To cover all possible transitions in the absorbing nucleus, the energy of the source radiation is modulated by using the Doppler effect, such that the emitted radiation has an energy E v) = Eo(l + vjc). For Fe the required velocities fall in the range (1 to t-1 cm s k In Mossbauer emission spectroscopy, the sample under investigation is the source, and a single line absorber is...

Fig. 2.6 Schematic illustration of a Mossbauer transmission experiment in five steps. The Absorption bars indicate the strength of recoilless nuclear resonant absorption as determined by the overlap of emission and absorption lines when the emission line is shifted by Doppler modulation (velocities Uj,. .., 1)5). The transmission spectrum T v) is usually normalized to the transmission T oo) observed for v oo by dividing T(v)IT(oo). Experimental details are found in Chap. 3...

Mossbauer spectra are usually recorded in transmission geometry, whereby the sample, representing the absorber, contains the stable Mossbauer isotope, i.e., it is not radioactive. A scheme of a typical spectrometer setup is depicted in Fig. 3.1. The radioactive Mossbauer source is attached to the electro-mechanical velocity transducer, or Mossbauer drive, which is moved in a controlled manner for the modulation of the emitted y-radiation by the Doppler effect. The Mossbauer drive is powered by the electronic drive control unit according to a reference voltage (Fr), provided by the digital function generator. Most Mossbauer spectrometers are operated in constant-acceleration mode, in which the drive velocity is linearly swept up and down, either in a saw-tooth or in a triangular mode. In either case. 

Most Mossbauer spectrometers use triangular velocity profiles. Saw-tooth motion induces excessive ringing of the drive, caused by extreme acceleration during fast fly-back of the drive rod. Sinusoidal operation at the eigen frequency of the vibrating system is also found occasionally and... 

Fig. 3.2 Triangular velocity reference signal top) and drive error signal bottom) of a Mossbauer drive operating in constant acceleration mode. The error signal is taken from the monitor output F of the drive control unit (see Fig. 3.1). Usually it is internally amplified by a factor of 100. Here, the deviations, including hum, are at the 2%o level of the reference. The peaks at the turning points of the triangle are due to ringing of the mechanical component, induced by the sudden change in acceleration (there should be no resonance line at the extremes of the velocity range)...

A memory sweep is initialized when the MCA receives a start pulse from the function generator at the trigger input (7). The start pulse is synchronized with the sweep of the reference voltage (Vr) for the Mossbauer drive. It opens the first MCA channel when the source velocity passes through the minimum (cf. Fig. 3.3). After this start trigger, a train of 512 channel advance pulses follows with exact delay times of about 100 ps each. On receiving such a channel advance pulse, the... 

Since the actual motion of the Mossbauer drive, as for any frequency transmission system, can show phase shifts relative to the reference signal, the ideal folding point (FP) of the raw data in terms of channel numbers may be displaced from the center at channel number (N — l)/2 (= 255.5 in the example seen earlier). The folding routine must take this into account. Phase shift and FP depend on the settings of the feedback loop in the drive control unit. Therefore, any change of the spectrometer velocity tuning requires the recording of a new calibration spectrum. 

The calibration procedure is sufficiently accurate for Doppler velocities in the regime 0 to 10 mm s beyond this range, laser calibration is more suitable. Calibration with ot-iron, as described, can also be used for Mossbauer measurements with other isotopes, e.g., Ni, Au, and Ir, for which suitable standard absorbers are not available (provided that the Doppler velocity range of interest is not significantly greater than 10 mm s ). This, of course, requires that the spectrometer is temporarily equipped with a Co source and an a-iron absorber. 

The number of beatings in the output signal U t) can be recorded as a function of the channel number simultaneously to the Mossbauer spectrum (usually in a second part of the MCA memory). Accordingly, the number of beats stored in each channel per velocity sweep divided by the dwell time of the MCA channels yields the specific average velocity for each detection channel. 

Fig. 3.10 Variation of the spectrometer aperture as a function of the source motion for Mossbauer spectrometers operated in constant acceleration mode with triangular velocity profile, and the resulting nonlinear baseline distortion of the unfolded raw spectra. For simplicity a point-source is adopted, in contrast to most real cases (Rib mm active spot for Co in Rh)...

The Mossbauer spectrometer will typically divide the velocity scale into 256 channels. For a 0.93 GBq source (25 mCi), the total count rate of photons arriving at the detector and having the proper pulse-height is usually about C = 20,000 counts s Only about 85% of these will be 14.4 keV radiation the others are... 

Fig. 3.16 Schematic drawing of the MIMOS II Mossbauer spectrometer. The position of the loudspeaker type velocity transducer to which both the reference and main Co/Rh sources are attached is shown. The room temperature transmission spectrum for a prototype internal reference standard shows the peaks corresponding to hematite (a-Fe203), a-Fe, and magnetite (Fe304). The internal reference standards for MIMOS II flight units are hematite, magnetite, and metallic iron. The backscatter spectrum for magnetite (from the external CCT (Compositional Calibration Target) on the rover) is also shown...

As discussed in Sects. 3.1.1-3.1.3, successful acquisition of Mossbauer spectra depends on accurate knowledge of the relative velocity of the source and sample. External vibrations that impart differential velocity components to the source and sample would degrade the quality of the Mossbauer spectrum. This degradation... 

Fig. 3.19 Schematic illustration of the measurement geometry for Mossbauer spectrometers. In transmission geometry, the absorber (sample) is between the nuclear source of 14.4 keV y-rays (normally Co/Rh) and the detector. The peaks are negative features and the absorber should be thin with respect to absorption of the y-rays to minimize nonlinear effects. In emission (backscatter) Mossbauer spectroscopy, the radiation source and detector are on the same side of the sample. The peaks are positive features, corresponding to recoilless emission of 14.4 keV y-rays and conversion X-rays and electrons. For both measurement geometries Mossbauer spectra are counts per channel as a function of the Doppler velocity (normally in units of mm s relative to the mid-point of the spectrum of a-Fe in the case of Fe Mossbauer spectroscopy). MIMOS II operates in backscattering geometry circle), but the internal reference channel works in transmission mode...

Fig. 3.23 Left-. Calculated relationship between the thickness of an alteration rind and/or dust coating on a rock and the amount of 15.0-keV radiation absorbed in the rind/coating for densities of 0.4, 2.4, and 4.0 g cm [57]. The bulk chemical composition of basaltic rock was used in the calculations, and the 15.0 keV energy is approximately the energy of the 14.4 keV y-ray used in the Mossbauer experiment. The stippled area between densities of 2.4 and 4.0 g cm is the region for dry bulk densities of terrestrial andesitic and basaltic rocks [58]. The stippled area between densities of 0.1 and 0.4 g cm approximates the range of densities possible for Martian dust. The density of 0.1 g cm is the density of basaltic dust deposited by air fall in laboratory experiments [59]. Right Measured spectra obtained on layered laboratory samples and the corresponding simulated spectra, from top to bottom 14.4 keV measured (m) 14.4 keV simulated (s) 6.4 keV measured (m) and 6.4 keV simulated (s). All measurements were performed at room temperature. Zero velocity is referenced with respect to metallic iron foil. Simulation was performed using a Monte Carlo-based program (see [56])...

One Mossbauer spectrum consists of 512 velocity channels (3 bytes per channel). One temperature interval consists of five Mossbauer spectra (one for each detector). There are 13 temperature intervals with selectable width. Thus, MIMOS II can accumulate simultaneously up to 65 Mossbauer spectra during one experiment session on Mars. All Mossbauer, energy, engineering, and temperature data taken during this session are stored in a volatile SRAM (Static Random Access... 

During the mission, the magnetite CCT was measured in several runs to verify the functionality of MIMOS II. The well-known Mossbauer parameters of magnetite were used for velocity calibration, as shown in Fig. 3.22 for different temperatures. This kind of measurement was done in the laboratory with the flight units as a function of temperature to be used as a reference for the measurements on Mars. Figure 3.22 shows the Mossbauer spectra of the CCT at different mean temperatures. 

The isomer shift of a resonance line (or the centroid of a line multiplet) in an experimental Mossbauer spectrum in terms of the Doppler velocity (mm s ) necessary to achieve resonance absorption is given by... 

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