WDXRF Physics and Parameters

Physics of X-Rays
and
Instrument Parameters
1 Bruker Confidential 31/10/2018

Introduction
 Physics of X-rays:
What are they?

Origin?
Properties?
 Instrument Parameters:
 tube
 filter
 (sample: see Appendix)
 collimator + collimator mask
 crystal
 detector

Introduction
 1  tube: “Kramer”
I () =KiZ -1
 min 
Sample
“Duane and Hunt”

Filters
Collimators
h.c
E=

Tube d,   filter
Crystals
 sample
 collimator
Z, i, E  crystal
 Detectors
n = 2d sin “Bragg”
 detector

Physics of X-rays: What are they?
Energy-range (keV) Wavelength Type of radiation

-7
< 10 cm to km Radio - waves
<10
-3
m to cm Micro - waves
<10
-2
m to mm Infrared
0,0017 - 0,0033 37 – 75 nm Visible light
0,0033 - 0,1 12,5 – 37 nm Ultraviolet light
0,1-100 0,0125 – 12,5 nm X-rays
100 - 5000 0,0002 – 0,0125 nm Gamma radiation
1nm = 10Å = 10-9m = 10-6mm
XRF analysis covers the following energy- respective wavelength range:

E = 0.11 - 60 keV  = 11.3 - 0.02 nm
or
Elemental range from Berylium (Be) to Uranium (U)

Physics of X-rays: Origin
X-rays originate from the energy loss associated with the interaction of
high energy electrons with atoms
Continuous radiation
(white radiation or Bremsstrahlung)
Characteristic radiation
(photoelectric effect)

h.c 12,4
 min = =
V V

characteristic radiation photoelectric interaction
M K-Quant EK = EK-EL

L
K EK = EK-EM
L-Quant EL = EL-EM

EM = EM-EN
High Energy Photon
K-Quant

Derivation of the X-ray lines from shell transfers
Niels Bohr
Bohr‘s atom model

X-ray emission lines = electron transitions

K H
2    K-lines
L Li, ....., F
      L-lines
M Na, ....., Cl
M-lines
N K, ....., Br

CONTINUUM, COHERENT (RAYLEIGH) AND INCOHERENT (COMPTON) SCATTERING

FLUORESCENT YIELD
Concurrent process:
Emission of
Auger-Electrons
Np(useful )
FluorescentYield (w ) =
Np(total)
wk(B)  0-
wk(Fe)  0.
wk(Te)  0.86
Physics of X-rays: Properties
All these effects occur at the same time!

I = Io. exp -  . r . x
 Photo-electric effect
=0 r, 
 Absorption (by composite
I0 (0) I ()
material)
 Scattering: coherent
incoherent
 Diffraction
 >0

sample
Rayleigh scattering (elastic)

Compton scattering (inelastic)
Y
0 c
- collimator slit
- analyser crystal
- detector
c-0 = 0.0243 (1 -cos ) in Å

Diffraction:
 coherent scatter from the different crystalline phases in the material
 reinforcement of the scattered waves takes place
PHASE ANTI-PHASE
 Bragg’s Law has to be fulfilled: n = 2d sin

Instrument Parameters: the tube
 Design: End-Window (or Side-Window)
 Anode material
 Window material
   1 
 Excitation kV, mA I ( ) = KiZ  - 1  2 
  min    
 Cooling

Tube head cooling

Water-inlet for cooling the anode
Ring-shaped cathode
Electron beam
thin Beryllium window 75m or 125m
X-ray beam
   1 
I ( ) = KiZ  - 1  2 
  min    
INFLUENCE OF THE ANODE MATERIAL
min.

   1 
I ( ) = KiZ  - 1  2 
INFLUENCE OF THE CURRENT   min    
Imax
min.

   1 
I ( ) = KiZ  - 1  2 
  min    
INFLUENCE OF THE KILOVOLTAGE
Imax
min.

Instrument Parameters: the filters
ADVANTAGES:
 Exclude tube lines
 Improve the peak to background ratio
 Suppression of spectral impurities from the tube spectrum
 Different types (Cu, Al,...) and varying thickness (10- 800 m) of filters
are available to select the optimum settings

Cu filter 200m to exclude the Rhodium tube lines

Use of an Al 100m film to improve the Peak-to-Background ratio
Sr KA1
LiF220
0,15 degree collimator Ip/Ib = 80 kcps/2,2 kcps = 36
50kV/50mA
3 Ib
Black: 100m Al filter LLD = *
Red: No filter s t
Ip/Ib = 36 kcps/0,8 kcps= 45

Sr KB1/3
Ip/Ib = 32,0 kcps/2,6 kcps = 12,3
Ip/ Ib = 14,7 kcps/1,09 kcps = 13,5 Rb KA1

Ip/Ib = 5,30 kcps/1,45 kcps = 3,60
Ip/Ib = 2,50 kcps/0,55 kcps = 4,55
<30.73 Y : 0.181 to 86.32 40.926>

8

Instrument Parameters: Sensitivity
The sensitivity in combination with the resolution can

depend on 2 parameters:
 the collimator or soller slit
 reflection efficiency of the crystal
The sensitivity can often be increased at the expense of

the resolution (separation between the peaks) and vice versa

Instrument Parameters: the
collimators
 The collimator is mostly preceded by a collimator mask
 The mask hides the sample cup radiation comes mainly from
the sample
 Different mask sizes (8, 18, 23, 28 and 34mm):

 different sample sizes
 improve cup masking
 Collimator:
 diverges secondary X-ray beam
 finer improves resolution but less intensity
 different sizes: 0.12, 0.23, 0.46, 1 and 2 degree (°)

collimators
IN
0,46 degree
0.23 degree
OUT
1 degree 2 degree

collimators
Improving the resolution by means of a collimator
0.46 degree collimator

0.15 degree collimator Cr KB1
Cr KB1
Mn KA1
Mn KA1
<61.21 Y : 0 to 362.5 kcps KCps 63.931>

9

Instrument Parameters: the Crystals
POLYCHROMATIC MONOCHROMATIC
' AC '
= sin 
d
' AC' = d sin 
' ACB' = 2d sin 
' ACB' = n Amplification
n = 2d sin  n = 1, 2, 3, ...... (Reflection order)

Crystal Material Application for Elements 2d–value [nm]
LiF(420) Lithiumfluoride from Co KB 0.1801

LiF(220) Lithiumfluoride from V 0.2848
LiF(200) Lithiumfluoride from K 0.4028
Ge Germanium P, S, Cl 0.653
InSb Indiumantimonide Si 0.7481
PET Pentaerythrit Al - Ti 0.874
AdP Ammonium dihydrogen Mg 1.0648
phosphate
TlAP Thalliumhydrogenphtalate F, Na 2.5760
OVO-55 Multilayer (W/Si) (C) O - Si 5.5
OVO-160 Multilayer (Ni/C) B, C, N 16
OVO-N Multilayer (Ni/BN) N 11
OVO-C Multilayer (V/C) C 12
OVO-B Multilayer (Mo/B4C) B (Be) 20

Improving the resolution by means of a crystal
LiF200 Cr KB1
240
230 LiF220
220
210
200
190
180
170
160
150
140
Lin (KCps)
130
120
Cr KB1
110
100
90
Mn K1
80
70
60
50
40
Mn K1
30
20
10
6. 04 6. 03 6. 02 6. 01 6. 00 5. 99 5. 98 5. 97 5. 96 5. 95 5. 94 5. 93 5. 92 5. 91 5. 90 5. 89 5. 88 5. 87 5. 86 5. 85 5. 84 5. 83 5. 823
E - Scale
Immediate Measurement - File: LiF200_0,46C.ssd - - 2Th.0: 61.200 - 2Th.1: 63.868 - WL.0: 2.050 - WL.1: 2.130 - Step Size: 0.046 - Time.: 0.600 - Crystal: LiF200 - Collimator: 0.46 degr. - Filter: none - Mask: 34 mm - kV: 50 - mA: 81
Operations: Import
Immediate Measurement - File: LiF220_0,46C.ssd - - 2Th.0: 89.400 - 2Th.1: 98.692 - WL.0: 2.003 - WL.1: 2.161 - Step Size: 0.046 - Time.: 0.200 - Crystal: LiF220 - Collimator: 0.46 degr. - Filter: none - Mask: 34 mm - kV: 50 - mA: 81
29 Bruker Confidential
Operations: Import 31/10/2018
Instrument Parameters: the detectors
 Detectors convert X - ray photons into measurable voltage pulses

 A range of detectors is required to cover the
wavelength range 0.012nm - 12nm (100 - 0.1 keV):
 Gas proportional detectors: 0.08nm - 12nm (15 - 0.1 keV)
 Scintillation detector: 0.012nm - 0.15nm (100 - 8 keV)
 Output pulse and energy incoming X-ray photon are proportional

Identification

Instrument Parameters:
the sealed proportional counter
Ar + 10% CH4 HV: + 1400 V - 2000 V

+ Anode wire +
Ar KA+ DE Ar++e-
e- e- e-
X-rays Pulse

Instrument Parameters:
the scintillation counter
Photo multiplier
NaI - crystal
X-ray quant
Photo cathode
High voltage

Some characteristics
 The Pulse Height Analysis or

Distribution (PHA/PHD)
Zn-K peak
 The Full Width at Half
00% E = 8.6 keV
Maximum (FWHM)
 The Resolution (R):
gas proportional: 15%
scintillation: 51%
FWHM: 49 %
Lower Higher Discrimination Window

Limit Limit
Y : 0 to 31.33 kcps
<10 200>

PHA = Pulse Height Analysis
Evaluation of the energy-distribution is very important

as several “non-analytical” signals may enter the detector:
 electronic noise
 escape peak
 higher order peaks
 crystal fluorescence
The next slides will show some examples based on Flow

Counter signals (Scintillation counter signals are generally
spoken straightforward apart from eventual Iodium crystal
fluorescence from the NaI crystal)

Mn-KA Escape Peak in Stainless Steel

Mn-KA
= 100% E Mn-KA = 5.9 keV
E Ar-KA = 2.96 keV
E Escape Mn-KA= (5.9 -2.96) keV = 2.94 keV
Electronic noise
Mn-KA
Escape Peak = 49%
<0 Y : 0 to 4.085 KCps 300>

Mg-KA in Cement
Mg-KA
= 100% E Mg-KA = 1.3 keV
E Ca-KA = 3,7 keV
E Ca-KA Escape peak = 0.7 keV
E Si-KA/B = 1.7/1.8 keV
E W-M = 1.8 keV
3 rd order Ca-KA
Si-K and W-M from OVO-55
= 285%
Electronic Noise = 135%
3 rd order Ca-KA
Escape peak = 55%
<0 Y : 0 to 1.308 KCps 340>

P-KA in Limestone with Ge crystal

80
P-KA
= 100% E P-KA = 2.0 keV
E Ge-LA = 1.2 keV
Ge X-tal fluorescence
= 60%
<10 Y : 0 to 0.087 KCps 300>

P-KA in Limestone with OVO-55 crystal
2nd order Ca-KA

= 185%
E P-KA = 2.0 keV
E Ca-KA = 3,7 keV EXERCISE!
E Ca-KA Escape peak = 0.7 keV
E Si-KA/B = 1.7/1.8 keV
E W-M = 1.8 keV
Electronic Noise
Si-K and W-M from OVO-55
= 90%
2nd order Ca –KA

Escape peak = 35%
P-KA
= 100%
<10 Y : 0 to 1.275 KCps 300>

Summary
 A lot of physics take place before we come to a final result: the better
you understand them, the better you will understand and control the
XRF technique
 Instrument parameters can be used to improve your final results
 It is important to understand both physics and the application of the
instrument parameters in order to set up good calibrations which give
you precise and accurate results

Appendix: The Sample
Introduction
 A bad sample preparation can lead to a large error in XRF-analysis

 Specify your analytical goals before beginning a specimen preparation
method as several effects may and do take place:
 penetration of X-rays (information depth, shadow effect)
 grain- or particle size effect
 crystallographic- or mineral effect
 inter-element effect

Penetration- and Information Depth
Penetration Depth
Information or Critical Depth
SURFACE TREATMENT !
high energy photons

Grain- or particle size effect
SiO2 analysed layer

Al2O3
ISi= f (NpSiO2)Volume
Analysed layer = homogeneous distribution
IAl = f (NpAl2O3)Volume

Crystallographic- or mineralogical effect
loose powders pressed powders

SiO2
analysed layer
AlxSiyOz
ISi= f ((NpSiO2)+(NpAlAlxSiyOz ))Volume

SSiO2(kcps/%)<>SAlxSiyOz
IAl = f (NpAlxSiyOz)Volume

Inter-element effect
Tube ENHANCEMENT ABSORPTION Detector
Normal Ni x-ray
Alpha NiFe
Gamma NiFe,Cr
Cr
Fe
Ni
Stainless Steel

 (cm2/g) Stainless Steel
Ni-K Fe-K Cr-K
Ni K-absorption Fe K-absorption Cr K-absorption

edge edge edge
Ni-K Fe-K Cr-K
 (Å)
1.4 1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2 2.3 2.4 2.5


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Physics of X-Rays

1 Bruker Confidential 31/10/2018

What are they?

2 Bruker Confidential 31/10/2018

3 Bruker Confidential 31/10/2018

Energy-range (keV) Wavelength Type of radiation

1nm = 10Å = 10-9m = 10-6mm

XRF analysis covers the following energy- respective wavelength range:

4 Bruker Confidential 31/10/2018

5 Bruker Confidential 31/10/2018

6 Bruker Confidential 31/10/2018

characteristic radiation photoelectric interaction

M K-Quant EK = EK-EL

L-Quant EL = EL-EM

7 Bruker Confidential 31/10/2018

Bohr‘s atom model

8 Bruker Confidential 31/10/2018

X-ray emission lines = electron transitions

9 Bruker Confidential 31/10/2018

CONTINUUM, COHERENT (RAYLEIGH) AND INCOHERENT (COMPTON) SCATTERING

10 Bruker Confidential 31/10/2018

All these effects occur at the same time!

12 Bruker Confidential 31/10/2018

Rayleigh scattering (elastic)

c-0 = 0.0243 (1 -cos ) in Å

13 Bruker Confidential 31/10/2018

 Bragg’s Law has to be fulfilled: n = 2d sin

14 Bruker Confidential 31/10/2018

 Design: End-Window (or Side-Window)

15 Bruker Confidential 31/10/2018

Tube head cooling

thin Beryllium window 75m or 125m

17 Bruker Confidential 31/10/2018

18 Bruker Confidential 31/10/2018

19 Bruker Confidential 31/10/2018

 Improve the peak to background ratio

 Suppression of spectral impurities from the tube spectrum

20 Bruker Confidential 31/10/2018

Cu filter 200m to exclude the Rhodium tube lines

21 Bruker Confidential 31/10/2018

Use of an Al 100m film to improve the Peak-to-Background ratio

Ip/Ib = 36 kcps/0,8 kcps= 45

Ip/Ib = 32,0 kcps/2,6 kcps = 12,3

Ip/ Ib = 14,7 kcps/1,09 kcps = 13,5 Rb KA1

<30.73 Y : 0.181 to 86.32 40.926>

22 Bruker Confidential 31/10/2018

The sensitivity in combination with the resolution can

The sensitivity can often be increased at the expense of

23 Bruker Confidential 31/10/2018

 The collimator is mostly preceded by a collimator mask

 Different mask sizes (8, 18, 23, 28 and 34mm):

24 Bruker Confidential 31/10/2018

25 Bruker Confidential 31/10/2018

0.46 degree collimator

<61.21 Y : 0 to 362.5 kcps KCps 63.931>

26 Bruker Confidential 31/10/2018

n = 2d sin  n = 1, 2, 3, ...... (Reflection order)

27 Bruker Confidential 31/10/2018

Crystal Material Application for Elements 2d–value [nm]

LiF(420) Lithiumfluoride from Co KB 0.1801

28 Bruker Confidential 31/10/2018

Improving the resolution by means of a crystal

 Detectors convert X - ray photons into measurable voltage pulses

 Gas proportional detectors: 0.08nm - 12nm (15 - 0.1 keV)