X-Ray Diffraction - PANalytical · © 2019 Malvern Panalytical l X-Ray Diffraction Analysis of crystalline materials Singapore Workshop 01 Nov 2019

$Page 1: X-Ray Diffraction - PANalytical · © 2019 Malvern Panalytical l X-Ray Diffraction Analysis of crystalline materials Singapore Workshop 01 Nov 2019$
© 2019 Malvern Panalytical Co

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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

http://www.google.com.sg/url?sa=i&rct=j&q=powder+samples&source=images&cd=&cad=rja&docid=O4TYr6BswM6CiM&tbnid=NpDyYl-bfS7nRM:&ved=&url=http://www.theodoregray.com/periodictable/Elements/024/index.s14.html&ei=SR9tUamEE8vwrQf7voDgDw&bvm=bv.45175338,d.bmk&psig=AFQjCNE85S9-l6Mvuz5ZfHjzysKh5ebEDg&ust=1366192329797031

http://www.google.com.sg/url?sa=i&rct=j&q=nano+gold+solution&source=images&cd=&cad=rja&docid=N9xmtDDIKRVJtM&tbnid=I-CQ0Zcc5AvBJM:&ved=&url=http://www.mrsec.wisc.edu/Edetc/background/quantum_dots/&ei=yxZtUeb-IcnirAeC7IDwBA&bvm=bv.45175338,d.bmk&psig=AFQjCNEg-6Cz9DJU7nCNmI5BgBXalwcanw&ust=1366190156074305

http://www.google.com.sg/url?sa=i&rct=j&q=thick+coatings&source=images&cd=&cad=rja&docid=LtpVUmZ15Mf4OM&tbnid=bVFyOPzweC-atM:&ved=&url=http://phys.org/news/2012-10-spray-paint-ultrathin-coatings-atoms-difference.html&ei=fu1sUZDHAoajiAfck4HIAw&bvm=bv.45175338,d.aGc&psig=AFQjCNH892e6nSz9XTuwCx3-8gst_z1c0w&ust=1366179582573960

http://www.google.com.sg/url?sa=i&rct=j&q=metal+block&source=images&cd=&cad=rja&docid=8SmlTNX1F2eX9M&tbnid=U8OX49-V1tjMbM:&ved=&url=http://www.queenslandbeadcompany.com.au/index.php?cPath%3D478_492&ei=2yJtUcKNA5DirAf2vIGYAQ&bvm=bv.45175338,d.bmk&psig=AFQjCNFrZDb2cp_oeoIxJehmwyRkGX4_ew&ust=1366193243737729


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XRD from powder crystals

• X-ray Powder Diffraction (XRPD)

5

http://www.google.com.sg/url?sa=i&rct=j&q=powder+XRD+images&source=images&cd=&cad=rja&docid=n-4mcufsJmB5EM&tbnid=uj1Wh2NyQePPKM:&ved=0CAUQjRw&url=http://chemwiki.ucdavis.edu/Analytical_Chemistry/Instrumental_Analysis/Diffraction/Powder_X-ray_Diffraction&ei=i4NiUcGmEYjtrQfKw4C4Dg&bvm=bv.44770516,d.bmk&psig=AFQjCNGWONg7rameFJmIONwQkKH6McQVpg&ust=1365496539351106


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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

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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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Co

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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

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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


Type phase ID and measurement program


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Step 3


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


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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X-Ray Diffraction - PANalytical · © 2019 Malvern Panalytical l X-Ray Diffraction Analysis of crystalline materials Singapore Workshop 01 Nov 2019

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