1. Corpuscular induced and X-ray or γ -ray induced fluorescence NON DESTRUCTIVE CHEMICAL ANALYSIS Notes by: Dr Ivan Gržetić, professor University of Belgrade – Faculty of Chemistry

2. Dual nature of the microscopic material In 1924, Louis de Broglie suggested that just as light exhibits wave and particle properties, all microscopic material particles such as electrons, protons, atoms, molecules etc. have also dual character. They behave as a particle as well as wave. Radiation with enough energy to knock electrons out of atoms and produce ions is called ionizing RADIATION and includes particles (protons, alpha particles, beta particles, accelerated ions) and rays (x-rays and gamma rays).

3. Induced X-ray florescence Primary (incidet) radiation that can induce X-ray fluorescence could be dividet into three major groups: ◦ Corpuscular induced fluorescence ◦ X-ray induced fluorescence (wave induced) ◦ γ -ray induced fluorescence (wave induced)

4. Corpuscular induced fluorescence

5. Electrons, protons, alpha particles or ions The radiation associated with subatomic particles, such as electrons, protons, alpha particles or ions, which travel in streams at various velocities. All such particles have definite masses and have radiation properties very different from those of electromagnetic radiations, which have no mass and travel as waves at the speed of light.

6. Electron induced X-ray fluorescence Common particles used for induced fluorescence are electrons and protons. Electron induced X-ray fluorescence is tightely bond to instruments like electron microscopes equiped with appropriate spectrometers for x-ray detection.

7. Scanning electron microscope - SEM

8. SEM with EDS and WDS EDS – Energy dispersive spectrometer WDS – Wavelength dispersive spectrometer

9. Electron sample intereaction

10. SAMPLE and SEM SIGNALS Backscattered electrons are electrons which have been emitted from the primary beam and have reacted elastically with the sample's atoms. They are sent back almost in the same direction as the one they came from, and with very little energy loss. Chemical elements that have a high atomic number produce more backscattered electrons than the ones that have a low atomic number. The areas of the sample with a high atomic number will thus look whiter than the ones with a low atomic number (high phase contrast).

11. SAMPLE and SEM SIGNALS Secondary electrons are emitted when the primary beam that has lost a part of its own energy, excites atoms of the sample. The secondary electrons have a little energy (about 50 eV) divided up on a large spectrum. Pictures obtained with the secondary electrons mostly represent the topography of the sample and they have very little phase contrast.

12. SAMPLE and SEM SIGNALS X-ray emision is electromagnetic radiations induced by primary (incident) radiation. The energy of the secondary X-rays produced from atomes present in the sample in SEM are usualy between 0.5 et 30KeV. Auger electrons Continuum...

13. SAMPLE and SEM SIGNALS Intereaction volumen, depth of signal and resolution

14. X-ray induced fluorescence

15. Sample X-ray Intereaction

16. Saturation Depth or Penetration Depth The deeper the X-ray enters the sample, the more it interacts with the sample’s atoms. An increasing portion of the X-ray is absorbed by the sample until a specific depth is reached beyond which the primary X-ray light can no longer penetrate. This also applies to the fluorescent light that must exit the sample in order to be detected. The lowest detectable sample layer is called the saturation depth. The saturation depth depends on the intensity of the X-rays, the wavelength (i.e., the type of detected atom) and the density of the sample’s surroundings (the matrix). If different elements are analyzed in the same surroundings, the saturation depth increases according to the atomic number of the element in question.

17. Saturation Depth or Penetration Depth

18. Table of Saturation Depth or Penetration Depth 28000 μm = 0,028 m = 28 mm ; (1 μm = 10 -6 m) ; 3 mm = 3000 μm

19. Difference between electron and X- ray impact volumen

20. Recommondation The thicknes of the bulk sample should be minimum 3 mm (5 mm). Thicker bulk samples are prefared for samples made of light elements (10-15 mm minimum). Thin layers and film samples are treated totaly different from bulk samples.

21. γ -ray induced fluorescence

22. Radioactive sources γ -ray induced fluorescence is usualy used for Field-portable x-ray fluorescence (XRF) also known as Hand held X-ray analyser. The X-ray emitting sources usually contain nuclides that decay by means of the electron-capture mechanism. During the decay, a inner shell electron is captured by the neutron- deficient nucleus, transforming a proton in a neutron. This results in a daughter nuclide that has a vacancy in one of its inner shells, which results in the emission of corresponding characteristic radiation. For example, when a 55Fe-nucleus (26 protons and 29 neutrons) captures a K-electron and becomes a 55Mn nucleus, a Mn K-L 3,2 (Mn-K α ) or KM 3,2 (Mn-K β ) photon will be emitted.

23. Radioactive sources An instrument may contain one or more of the following radioactive isotopes:

24. Cadmium (Cd-109) source The 109Cd source emits X-rays with energies of 22 and 25 keV when it decays to 109Ag in the two-step nuclear process of electron capture and internal conversion. In addition, a small portion (3.8%) of its photon output is emitted at 88 keV. The 22- and 25- keV emissions of this isotope may be used for the K- shell excitation of atomic numbers 22 (Ti) through 44 (Ru) and L-shell excitation of atomic numbers 67 (Ho) through 94 (Pu).Additionally, an 88-keV co output will excite K-shells up to lead. The isotope has a half-life of 1.24 years, meaning that after this time the source activity is half its original value.

25. Americium (Am-241) The 241Am is a source of 59.5 keV X-rays allowing for the excitation of higher atomic number elements. This isotope has generally been used for the K-shell excitation of atomic numbers 45 (Rh) through 66 (Dy). However, 241Am is also a source of lower excitations at approximately 13.95 and 17.7 keV (the neptunium L-lines). This permits all elements from about atomic number 22 (Ti) through 94 (Pu) to be analyzed effectively with only one radioisotope source. Furthermore, the americium isotope has a half-life of 432 years and therefore never requires replacement.

26. Useful range of X ray radioactive sources The range of elements that can be usefully analyzed by means of various radioactive X-ray sources.

27. THE END