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Clay Sample Prep and Interp

This document discusses methods for preparing and analyzing clay mineral samples using x-ray diffraction (XRD). It describes the different types of clay minerals including kaolinite, smectite, illite, chlorite, and their structures. It outlines sample preparation techniques such as disaggregation, chemical pretreatments, particle size separation, and oriented mounting methods. It provides information on interpreting XRD patterns to identify clay minerals based on d-spacing values and diagnostic peaks. It also discusses challenges with mixed layered clays and provides guidance on quantitative clay mineral analysis.

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walid dawoud
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109 views35 pages

Clay Sample Prep and Interp

This document discusses methods for preparing and analyzing clay mineral samples using x-ray diffraction (XRD). It describes the different types of clay minerals including kaolinite, smectite, illite, chlorite, and their structures. It outlines sample preparation techniques such as disaggregation, chemical pretreatments, particle size separation, and oriented mounting methods. It provides information on interpreting XRD patterns to identify clay minerals based on d-spacing values and diagnostic peaks. It also discusses challenges with mixed layered clays and provides guidance on quantitative clay mineral analysis.

Uploaded by

walid dawoud
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Clay Mineral XRD Sample Preparation

and Interpretation
Ceramic XRD patterns

Connie Constan, guest lecture


EPS 400, 04/04/2012
What are clays?
• Fine-grained
• Earthy
• Plastic when moist

• Group of minerals
• Category of rocks and soils
• Particle-size grade (<2µm)
Phyllosilicates
• kaolin group (two-layer clays)
• smectite group (three-layer, expanding lattice)
• illite group (three-layer, non-expanding)
• chlorite group (three-layer with interlayer cations)

Images from Railsback's


Some Fundamentals of
Mineralogy and
Geochemistry
Hydrous-Magnesian Clays
• Lath structure clays
• Chain-like arrangement

• palygorskite group
• sepiolite group
Sepiolite/Meerschaum pipe bowls
Sample Preparation

• Constraints
– Supplies and equipment
available
USGS Open-File Report 01-041
– Purpose of analysis
– Material itself
– Your knowledge and
ingenuity

USGS Open-File Report 01-041


Disaggregate the Rock

Mortar and Pestle Utrasonic Probe

Waring Laboratory Blender McCrone Micronising Mill


Chemical Pretreatments
• Removal of carbonates
These acids can cause burns. Wear
– Acetic acid goggles, plastic gloves, and an apron
while working with these chemicals.
• Removal of organics
– Hydrogen peroxide

• Removal of sulfates
• Removal of iron oxides

USGS Open-File Report 01-041


• Cation saturation
Particle Size Separation
• Methods
– Decantation
– Centrifugation

• Settling times USGS Open-File Report 01-041

– Stoke’s Law

• Dispersant/deflocculant
– sodium
hexametaphosphate USGS Open-File Report 01-041
Oriented Methods
• Why?

USGS Open-File Report 01-041

Velde and Druc 1999: Figure 3.8


Glass Slide
• Advantage
– Quick
• Disadvantage Moore and Reynolds Figure 6.1

– All
• Level of skill needed
– Low
• Application
– Qualitative analysis
USGS Open-File Report 01-041
Smear Mount
• Advantage
– Quick, moderately
homogenous
• Disadvantage
– Most USGS Open-File Report 01-041

• Level of skill needed


– Moderate
• Application
– Clay and nonclay
minerals USGS Open-File Report 01-041
Filter Transfer
• Advantage
– Homogenous aggregate
• Disadvantage
– Fair intensities
• Level of skill needed
– Moderate
• Application
– Quantitative
representation

Images from USGS Open-File Report 01-041


Porous Plate
• Advantage
– Best intensities
• Disadvantage
– Inhomogeneous
aggregate Moore and Reynolds Figure 6.4

• Level of skill needed


– High
• Application
– Crystal structure studies

Porous Ceramics
www.sentrotech.com
Ethylene Glycol Solvation

Images from USGS Open-File Report 01-041


Random Mount

• Why?

USGS Open-File Report 01-041


Moore and Reynolds Figure 6.5
New Instrumentation!
• Rigaku SmartLab • Rigaku Rapid II
– Nanomaterials – Mounted samples
– Thin films – Thin films
– Powder & bulk – Capillaries
– Metals & alloys – 2D detector/image plate
Microdiffraction
• Point Focus geometry in SmartLab system

CBO
CBO-f
Parabolic
Polycap

• Automated diffraction mapping in Rapid II system


General Principles of Identification
• Basal (00l) spacing

Illite Diffractogram Calculated X-ray diffraction pattern of antigorite


www.gly.uga.edu/schroeder/geol6550/CM11.htm www.gly.uga.edu/Schroeder/geol6550/CM07.html
Illite and Glauconite

Glauconite-rich sandstone

Moore and Reynolds Figure 7.3


Chlorite and Kaolinite

USGS Open-File Report 01-041

Moore and Reynolds Figure 7.4


Smectite

USGS Open-File Report 01-041

Moore and Reynolds Figure 7.8


Vermiculite

USGS Open-File Report 01-041

Moore and Reynolds Figure 7.7


Sepiolite, Palygorskite, Halloysite

• Sepiolite
6.9 deg 2θ

• Palygorskite
8.5 deg 2θ

• Halloysite
~20 deg 2θ

Scanning electron image of halloysite


www.gly.uga.edu/Schroeder/geol6550/halloysite.gif
Polytypes
• 1M and 2M1 most
common polytypes
– Use diagnostic hkl
reflections tables in
Moore and Reynolds
(Tables 7.5 to 7.7)

• Turbostratic Stacking
– Wide band at hk (13,20)
asymmetiric towards
wide angles in XRD

Figures from Meunier (2005: Figure 1.12)


Mixed-Layered Clays
• Illite/Smectite (I/S)
– Ethylene glycol solvation
– Reichweite ordering between
5 and 8.5 degrees 2θ
– Percent illite estimation from
value of Δ2θ
• Chlorite/Smectite (C/S)
– Expansion with ethylene glycol
solvation
– Expansion with Mg saturation
and glycerol solvation
Mixed-Layered Clays
• Chlorite/Vermiculite • Serpentine/Chlorite
– Ethylene glycol solvation – Broadening of odd-
– Mg saturation numbered peaks
– Glycerol solvation – Equation to determine
– Heat treatment percent serpentine
– Air-dried condition • Mica/Vermiculite
– Percent from Δ2θ – Heat treatment
• Kaolinite/Smectite – Mg saturation
– Ethylene glycol solvation – Glycerol solvation
– Heat treatment – Use low-angle reflection
(001/001) for percent
– Percent from Δ2θ and Reichweite ordering
Non-Clay Minerals
MINERAL TYPE SHOWN D SPACING ANGLE 2θ

Silicas α quartz 4.27, 3.342 20.8, 26.67

Feldspars K-spar, Plag 3.19, 3.24 27.95, 27.52

Zeolites solid solution series Approx. 8-9 <12

Carbonates Calcite, Dolomite 3.04, 2.89 29.43, 30.98

Sulfates Gypsum, Anhydrite 7.61, 3.50 11.7, 25.46


Quantitative Analysis
• Required Sample Characteristics
– Length
– Thickness
– Position
– Homogeneity

Figures from Moore and Reynolds (1997)


Quantitative Analysis
• Mineral Reference Intensities
• Peak Intensity Measurement
Smectite-rich I/S
• Peak Decomposition Well-crystallized illite (WCI)
Poorly-crystallized illite (PCI)

y
Two methods
Illite-rich I/S

FWHM Índice de Ku bler 4 6 8


°2θ, CuKα
Gharrabi et al., 1998 CCM, 46:79-88
Peak Decomposition
Righi and Elsass, 1996 CCM, 44:791-800

FWHM
8 9 10
°2Θ
Índice de Eberl y Velde
FWHM = full width at
half maximum
Clay Quantification
• The best diffraction peaks to use are as close
together as possible
• Avoid the low diffraction angle region
• Do not use external standards
• Need random orientation when both clay and
non-clay minerals are present in a single
sample
• Use integrated intensities and calculated
calibration factors
Clay Quantification

QUANTITATIVE X-RAY DIFFRACTION ANALYSIS OF CLAY-BEARING


ROCKS FROM RANDOM PREPARATIONS
Srodon et al 2001 Clays and Clay Minerals 49(6):514–528
My Research
• What clay minerals were
available locally?

• What clay minerals were


used in Gallina ceramics?

Natural Clays
Geology = seven formations

Ceramics
Archaeology = three types
My Results

Gallina Black-on-gray
ceramic sherd

Ceramic Qal Fm.


Estimated Original Firing Temperature

Clay pattern at each temperature: unfired, 300,


600, 750, and 900ºC
Summary
• “Identifying clay minerals for their diffraction
tracing is something of a Gestalt process, i.e.,
identifying the whole – being able to say that
it is an illite/smectite because it has an
illite/smectite pattern.”
(Moore and Reynolds 1997:296)

• In other words, you just have to learn what


the characteristic patterns look like for each
clay mineral and the mixed-layered clays.

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