X-Ray Diffraction - PANalytical · © 2019 Malvern Panalytical l X-Ray Diffraction Analysis of...
Transcript of X-Ray Diffraction - PANalytical · © 2019 Malvern Panalytical l X-Ray Diffraction Analysis of...
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X-Ray DiffractionAnalysis of crystalline materials
Singapore Workshop 01 Nov 2019
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XRD
• XRD investigates crystal forms
Crystal form investigation
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Crystalline materials
NaCl Aspirin Graphite
3
Orderly/repetitive arrangement of molecules
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Crystalline Materials
• Usually having large number of small crystals (crystallites) randomly oriented in 3D• Powder, Solids, Coatings (> 500 nm), polymers, paste, suspension
Some examples
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XRD from powder crystals
• X-ray Powder Diffraction (XRPD)
5
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XRD: Anatase & Hematite
Position [°2Theta] (Copper (Cu))
20 30 40 50 60
Counts
0
500
1000
0
200
400
600
Anatase
Hematite
RIR = 4.96
RIR = 2.83
TiO2 Powder
Fe2O3 Powder
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Position [°2θ] (Copper (Cu))
10 20 30 40 50 60 70
Counts
0
10000
20000
0
10000
20000
Rutile TiO2
Anatase TiO2
Crystal forms of same compound
7
Polymorphs
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(Crystal) Phase Identification
• PDF4++• Inorganics, polymers and
common organics
• PDF4 Organics• Organics
• COD: Free Inorganics
database
Using XRD databases
Position [°2Theta] (Copper (Cu))
20 30 40 50 60 70
Counts
0
1000
2000
3000 Minmix
Quartz
Hematite
Calcite
Fluorite
Corundum
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Phase Quantification
• Rietveld quantification
using crystal structure
information from the
database
Standardless
20 30 40 50 60 70
Counts
0
1000
2000
3000 Minmix
Quartz 19.2 %
Calcite 23.6 %
Corundum 23.1 %
Fluorite 17.1 %
Hematite 17.1 %
Rwp = 6.1120
050
-50
100
-100
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Amorphous FormsDisordered crystal
Position [°2θ] (Copper (Cu))
10 20 30
Counts
0
500
1000
SAMPLE-B
❖ Usually present in
Polymers, fibres, pharmaceuticals
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X-ray diffractionIn presence of amorphous form
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Liquid Crystals
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XRD application: Crystallite Size
Position [°2Theta] (Copper (Cu))24 26 28 30
Counts
0
10000
20000
30000
0
2000
4000
6000
8000
Silicon
TiO2
w=0.1
w=0.8
Peak List
= 0.1
= 0.8Size = 11.6nm
0
1.0x105
2.0x105
3.0x105
20 30 40 50 60 70 80
TiO2 Sample 1TiO2 Sample 2TiO2 Sample 3
2 Theta [deg]
Inte
nsity [counts
]
decreasing
size
Debye Sherrer Method
Williamson Hall Plot
Rietveld Method
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Application Examples
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Nickel ores
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Pyrrhotite
Pyrrhotite (Po) is a name used to denote a family of Fe-deficient
(and Ni bearing) sulfides with the general formula, Fe1-xS:
1. Hexagonal pyrrhotite (hpo)
2. Monoclinic pyrrhotite (mpo)
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hpo / mpo problems for ore beneficiation
• hpo is non-magnetic vs. mpo which is magnetic
→ creating a magnetic separation issue
• hpo oxidizes more readily than does mpo
→ creating problems in flotation cells
• hpo is slightly richer in Ni than mpo
→ hpo Ni ore $$$
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Position [°2Theta] (Cobalt (Co))
10 20 30 40 50 60 70
0
2000
4000
6000
8000
Counts
Pyrrhotite ratio by XRD
51 52
Counts
2000
4000
0
Sample A
Amphibole 20.5 %
Biotite 2.4 %
Monoclinic Po 50.4 %
Quartz 3.4 %
Plagioclase 7.0 %
Marcasite 1.9 %
Pentlandite 4.0 %
Hexagonal Po 2.5 %
Pyrite 1.1 %
Chalcopyrite 1.2 %
Ilmenite 0.1 %
Magnetite 0.4 %
Chlorite 4.5 %
Microcline 0.2 %
Epidote 0.6 %
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Cement with Fly-ash and Slag
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Analysis of polymers
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Crystalline to amorphous
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Analysis of polymers
22
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Catalysts
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Nano-crystalline phases
Position [°2θ] (Copper (Cu))20 30 40 50
Counts
0
2000
4000
6000
EtiAl_S-09
gamma-Al2O3 85.3 %
alpha-Al2O3 14.7 %
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XRD
• Empyrean: Floor standing Multi-applications
• Aeris: Compact XRD
Diffractometers
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Aeris Compact diffractometerSuited for industrial environments
• Same data quality as a floor standing system
• With similar speed of measurement
• External Sample loading• No optical path tampering
• Good dust protection
• Automation ready
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Step 1
19 November 2019Title of the presentation26
Place sample
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Step 2
19 November 2019Title of the presentation27
Type phase ID and measurement program
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Step 3
19 November 2019Title of the presentation28
Results
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various sample types
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• Belt Automation
• 6 position sample changer
• Quantitative results with RoboRiet routines
• Result transmission via LIMS (UAI)
Aeris
19 November 2019Title of the presentation30
Automation
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Quantitative phase ID
Crystallite size
Micro-strain
Crystallinity
Lattice parameters
Routine XRD
Structure refinement
Indexing
Structure solution
2D XRD
In situ XRD
Advanced XRD
Which XRD applications can you do on Aeris?
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In situ XRD (up to 500 ºC)
Sample holder: nickel or ceramics (Al2O3)
Sample size: 16 x 14 mm
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In situ XRD monitoring of a- transition in KNO3
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Phase transformation from a- to –phase of KNO3 observed
at ~ 130 °C (literature value is ~130 °C).
a - phase
- phase
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