X-ray Analyses of Ceramics: A look into how X-ray technology is utilized in the Ceramics

Jeremy Karr, Ph.D. Advanced Materials Characterization Workshop June 7, 2017

Outline

� Introduction

� X-ray Background/Theory

� Overview of Shimadzu X-ray Instruments� EDX-7000/8000� XRD-6100/7000

� Introduction to Ceramics

� Example Application of X-ray Techniques Used in Ceramic Analysis

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Who Am I?

� B.S. Ed. Emphasis in Physical Science – 2000

� Ph.D. Analytical Chemistry – 2008

� 6 Years Assistant Professor of Chemistry

� 4 Years Director of Research and Development –

AgSource Laboratories

� 11.5 Weeks as Field Technical Support Specialist for Materials Testing - Shimadzu

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Memorial Stadium

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• Electromagnetic radiation

• Wavelength is 0.01 ~ 100 Angstrom.

• Penetrates materials due to high energy

• The wavelength near inter-atomic distances in a crystal causes diffraction

What is the X-ray?

B.D. Cullity and S.R Stock, Elements of X-ray Diffraction (3rd Edition), Prentice Hall (2001)

How Do X-Rays Interact with Atoms?

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-Irradiating

X-ray

Ejected Electron

Fluorescent X-ray

Shimadzu X-ray Instruments

� Energy Dispersive X-ray Fluorescence � EDX-7000/8000

� Wavelength Dispersive X-ray Fluorescence � XRF-1800

� X-ray Diffraction Instruments� XRD-6100/700

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Features of Energy Dispersive X-Ray Fluorescence Spectrometers

� Sample forms can be solid, powder, or liquid.

� Nondestructive analysis, not requiring chemical pretreatment

� Capable of fast analyses (approx. 1 to 10 minutes)

� Extensive elemental measurement range (11Na to 92U)

� Extensive quantitative concentration range (ppm to 100 %)

� Does not require a standard sample, enabling simple quantitative analysis.

� Can also perform precise quantitative analysis using a standard sample.

� Capable of qualitative elemental analysis.

� The unit is compact (tabletop) and does not require cooling water facilities.

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Applications and Industries Where Used

Electrical/electronic materials� RoHS and halogen screening

� Thin-film analysis for semiconductors, discs,

liquid crystals, and solar cells

Automobiles and machinery� ELV hazardous element screening

� Composition analysis, plating thickness

measurement, and chemical conversion

coating film weight measurement for

machine parts

Ferrous/non-ferrous metals� Main component analysis and impurity

analysis of raw materials, alloys, solder, and

precious metals

� Composition analysis of slag

Mining� Grade analysis for mineral processing

Ceramics� Analysis of ceramics, cement, glass, bricks,

and clay

Oil and petrochemicals� Analysis of sulfur in oil� Analysis of additive elements and mixed

elements in lubricating oil

Chemicals� Analysis of products and organic/inorganic raw

materials� Analysis of catalysts, pigments, paints, rubber,

and plastics

Environment� Analysis of soil, effluent, combustion ash,

filters, and fine particulate matter

Pharmaceuticals � Analysis of residual catalyst during synthesis� Analysis of impurities and foreign matter in

active pharmaceutical ingredients

Agriculture and foods� Analysis of soil, fertilizer, and plants� Analysis of raw ingredients, control of added

elements, and analysis of foreign matter in foods

Others� Composition analysis of archeological samples

and precious stones, analysis of toxic heavy metals in toys and everyday goods

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Main Specifications

X-ray tube Max.: 50 kV, 1 mA, air-cooled, Rh target

Detector High-performance SDD detector (liquid nitrogen not required)

Elemental measurement rangeEDX-7000:

11Na to

92U

EDX-8000: 6C to

92U

Primary filters 5 types + OPEN, with automatic switching

Collimators 4 types, with automatic switching (1, 3, 5, and 10 mm dia.)

Sample observation

mechanismCMOS camera

Sample chamber dimensions

(W × D × H)300 mm ×××× 275 mm ×××× approx. 100 mm (radiuses excluded)

Body dimensions (W × D × H) 460 mm ×××× 590 mm ×××× 360 mm

Body weight Approx. 45 kg

SoftwareSimple analysis software (PCEDX-Navi)General analysis software (PCEDX-Pro)

Options Vacuum measurement unit

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Elements That Can Generally Be Analyzed with Fluorescent X-Rays

Energy Dispersive Type 11Na to 92U (With some models, 6C to 92U)

Wavelength Dispersive Type 4Be to 92U (With an analyzing crystal and detector combination)

Periodic Table of the Elements

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Appearance and Sample Chamber

Though the unit is compact, it is equipped with a large, vacuum-compatible sample chamber.During analysis, the blue LED on top is lit, so the instrument status can be checked even from another location.

W: 460 mm

Body dimensions (W × D × H)

460 mm × 590 mm × 360 mm

Easy-to-see LED indicators

Red: X-rays ON

Blue: Analyzing

Sample chamber dimensions (W × D × H)

300 mm × 275 mm × approx. 100 mmMagnified

12-Sample Turret

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Optical System

This is a bottom irradiation type optical system, in which X-rays are emitted from below the analysis sample. The primary filters, collimators, and sample observation camera are included as standard.

Collimator

Primary filters

X-ray tube

SDD detector

Analysis sample

Sample observation

camera

X-Ray Tube: Why Rhodium?

Why is rhodium used as the X-ray target?

• Rh K-rays are efficient at generatingfluorescent X-rays from heavy elements,

and the L-rays are efficient at generating

fluorescent X-rays from light elements

• Rh is rarely the subject of analysis

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Collimators and Sample Observation Camera

The collimator and sample observation camera are required for small sample and trace sample analyses.The camera image is saved automatically when analysis starts, and can also be checked from

the data.

� Four collimators (1, 3, 5, and 10 mm dia.)

� Sample observation camera

When 10 mm diameter is selected When 5 mm diameter is selected

(Trace sample cell used)

When 1 mm diameter is selected

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Primary Filters

The primary filter is effective for reducing continuous X-rays and characteristic X-rays from the X-ray tube.Five primary filters are provided as standard, enabling high-sensitivity analysis of an extensive

range of elements.

Filter #2 Filter #4 Filter #1

� Primary filters (5 types + OPEN)

RhL line

Background from continuous X-rays

RhK line

Filters

There are 5 filters available on the EDX-7000/8000, and they each have an effective energy range as seen below:

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Quantitation Functions

The following quantitation functions are included as standard.

� Calibration Curve Method� Highly accurate quantitation method using a standard sample

� FP Method (Bulk FP Method)� This method quantifies the sample using a theoretical intensity calculation. It can

quantify samples even without a standard sample.

� Film FP Method� This is suited to film thickness and composition analyses of plating and thin films.

� Background FP Method� This adds a theoretical intensity calculation of the scattered X-rays to the

conventional FP method. It is effective for improving the accuracy when quantifying low volume organic samples, and for film thickness measurements of

irregularly shaped plating samples.

What are Ceramics?

� Image search on Google

� Merriam-Webster Definition� of or relating to the manufacture of any product (such as earthenware, porcelain,

or brick) made essentially from a nonmetallic mineral (such as clay) by firing at a high temperature

� Clay� an earthy material that is plastic when moist but hard when fired, that is

composed mainly of fine particles of hydrous aluminum silicates and other minerals

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What are Ceramics?

� Wikipedia� an inorganic, non-metallic, solid material comprising metal, non-metal or

metalloid atoms primarily held in ionic or covalent bonds

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http://www.agicc.co.jp/abouts/2015020515162121.html

• Medical Equipment• Fuel Cells

• Auto Parts• Clothing (Deodorizers/Disinfectants)

• Electric Insulators

• Aerospace Industry

1986: A Bad Year for Ceramic Imports

� May: Williams and Sonoma Recall � 16,000 Earthenware Cazuela Cooking Pans Made in Spain

� July: Williams and Sonoma Recall� 2,000 Wine Jugs Made from Same Spanish Manufacturer

� September/October Pier 1 Recalls� 6,000 Earthenware Pitchers Made in Italy

� 1971 FDA Imposes Standards Governing Lead Release

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2010: Oriental Trading Company Recall

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� Voluntary Recall of 220,000 Ceramic Banks Due to High Lead Levels

2012: Enesco Recall

� Voluntary Recall of “Any Wine Will Do” Wine Goblets� Lead and Cadmium

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United States Custom and Border Protection� Imported Ceramic Tableware is not Prohibited or

Restricted

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Mexico India Hong Kong

China

Lead Release Testing Recommended

Or

Suggested for Decorative Purposes

How Can X-ray Techniques be Applied to the Study of Ceramics

� A Shimadzu White Paper Entitled: X-Ray Analysis of Ceramics by Dan Davis

� Utilized XRD and EDX Techniques

� XRD � Provided Information on Ceramic Starting Materials Composition and Identity

� EDX� Provided Contaminant Information on Finished Ceramic Product

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Analysis of Ceramic Starting Materials

� Starting Material of Ceramics – Clay� Needs to be

� Mined, Identified and Refined

� Ceramic Applications Call for Most Favorable Ratios of Specific Minerals

� XRD is Suited Perfectly for Identifying Elemental

Composition and Arrangement

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XRD Analysis of Clay

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Figure 1: X-Ray Diffraction of Bentonite Clay (top) and spectral reference of the minerals identified,

Montmorillonite, Quartz, Calcite, and Cristobalite

XRF Analysis of Impurities in Clay

� EDX Provides Quick Identification of Elemental Composition

� Qualitative – Provides Identification of Elemental Compositions (Na-U)

� Quantitative – Create a Calibration Curve with Known Standards

� Semi-Quantitative- Utilize Instrument Programmed Algorithms to Determine “Quantitative” Levels of Each Element (Na-U) Present in the Clay

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Figure 2: XRF scan of ceramic medical implant material with Iron impurity

Finished Ceramic Product Analysis

� Technique Needs to be Non Destructive

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Figure 4: Spectra of drinking mug where lead contamination is identified

Figure 5: Drinking Mug in XRF System

Conclusion

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� XRD (Qualitative)� Powder is Analyzed to Identify Elemental Components and Arrangements

� XRF (Qualitative/Quantitative)� Powder is Analyzed to Identify Elemental Components � Finished Product is Analyzed to Identify Impurities

� XRD and XRF Provide Different/Similar Information that Together Complete the Analysis Process

For Research Use Only. Not for use in diagnostic procedures.For Research Use Only. Not for use in diagnostic procedures.For Research Use Only. Not for use in diagnostic procedures.For Research Use Only. Not for use in diagnostic procedures.This presentation may contain references to products that are not available in your country.

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