Ebs 325 analytical chemistry laboratory introduction to x ray analysis
Sponsored Links
This presentation is the property of its rightful owner.
1 / 100

EBS 325 – Analytical Chemistry Laboratory Introduction To X-Ray Analysis PowerPoint PPT Presentation

  • Uploaded on
  • Presentation posted in: General

EBS 325 – Analytical Chemistry Laboratory Introduction To X-Ray Analysis. School of Materials & Mineral Resources Engineering, Engineering Campus, Universiti Sains Malaysia. By Mr. Samayamutthirian Palaniandy. OUTLINE. SAMPLING & SAMPLE PREPARATION. XRF. XRD.

Download Presentation

EBS 325 – Analytical Chemistry Laboratory Introduction To X-Ray Analysis

An Image/Link below is provided (as is) to download presentation

Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author.While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server.

- - - - - - - - - - - - - - - - - - - - - - - - - - E N D - - - - - - - - - - - - - - - - - - - - - - - - - -

Presentation Transcript

EBS 325 – Analytical Chemistry LaboratoryIntroduction To X-Ray Analysis

School of Materials & Mineral Resources Engineering,

Engineering Campus, Universiti Sains Malaysia.


Mr. Samayamutthirian Palaniandy





















X-RAY analytical errors


Sample preparation





  • A means by which units are taken from a

  • population in such a way as to represent the

  • characteristics of interest in that population.

FAQ about samples and sampling





The equipment does

what we want.


Our sampling

frequency is fine.

Reasons for poor procedures, equipment, and practices of SAMPLING.

Lack of knowledge of the consequences of poor


Lack of knowledge of the sampling theory.

Trying to save money.

Questions to be answer

before sampling

WHAT is being sampled?

WHY is the sample being taken?

WHO is taking the sample?

WHERE is the sample taken?

WHEN and with what frequency is the sample taken?

HOW is the sample taken?

HOW MUCH material is in the sample•?


Coning &








Paper cone

riffle splitter




Fractional Shoveling

Grab Sampling

Consist of taking a sample using scoop or spatula

by simply inserting the sampling device into the sample

container and removing an aliquot

Sample Mixing Flowing Liquids or Gases

A correct cross stream

sample may be

impossible to obtain.

A static mixer can reduce the Grouping

and Segregation Error.

Precision of Sub-sampling Methods

Gerlach, Dobb, Raab, and Nocerino, 2002 Journal of Chemometrics “Gy Sampling in experimental studies. 1. Assessing soil splitting protocols” 16, 321-328

Your decisions are only as good as your samples.

Your samples are only as good as your

sampling systems.

Your sampling systems are only as good as your audit and assessment.


X-RAY analytical errors


Sample preparation




Analytical errors – sampling

  • Sample must be representative of the process

  • Sampling must be reproducible (i.e. should be able to take identical duplicate samples)

Sample preparation methods





Low cost

Quality of sample preparation

The quality of sample preparation is at least as important as the quality of the subsequent measurements.

Quality of sample preparation

An ideal sample would be:

  • Representative of the material

  • Homogenous

  • Of infinite thickness

  • Without surface irregularities

  • With small enough particles for the wavelengths being measured






XRF only


XRD Working Concept

When a monochromatic x-ray beam with wavelength  is incident on the lattice planes in a crystal planes in a crystal at an angle , diffraction occurs only when the distance traveled by the rays reflected from successive planes differs by a complete number n of wavelengths. By varying the angle , the Bragg’s Law conditions are satisfied by different d-spacing in polycrystalline materials. Plotting the angular positions and intensities of the resultant diffraction peaks produces a pattern which is characterised of the sample. Where a mixture of different phases is present, the diffractogram is formed by addition of the individual patterns.

XRF Working Concept

In X-ray fluorescence spectroscopy, the process begins by exposing the sample to a source of x-rays. As these high energy photons strike the sample, they tend to knock electrons out of their orbits around the nuclei of the atoms that make up the sample. When this occurs, an electron from an outer orbit, or “shell”, of the atom will fall into the shell of the missing electron. Since outer shell electrons are more energetic than inner shell electrons, the relocated electron has an excess of energy that is expended as an x-ray fluorescence photon.  This fluorescence is unique to the composition of the sample. The detector collects this spectrum and converts them to electrical impulses that are proportional to the energies of the various x-rays in the sample’s spectrum.




























Sample types


Pressed powders

Fused beads



  • metal alloys, plastics & glass

  • relatively easy to prepare by cutting, machining, milling % fine polishing

  • Avoid smearing of soft metals (e.g. Pb)

  • Polishing may introduce contamination from the polishing material

  • do not have particle size problems

  • Surface needs to be flat

  • Surface needs to be homogeneous

  • Surface defects are more critical for light elements if good accuracy is required.

Pressed powders

  • Typical samples types that are prepared as pressed powders include rocks, soil, slag, cements, alumina, fly ash, etc.

  • Particle size of powder needs to be controlled for light element analysis

  • If necessary, powders are ground to achieve a particle size of < 50 µm

  • Grinding can be introduce contamination (e.g. Fe from a chrome steel mill)

  • Binding agents (e.g. wax or cellulose) can be used to increase sample strength to avoid breakage in the spectrometer

  • Ground powders are pressed into a solid tablet under pressure using a hydraulic press & 40 mm die

  • Relatively slow method (≈5 minutes per sample) but relatively low cost

  • Pressed powders suffer from particle size problems for light elements

    Preparation equipment needed includes:

  • Grinding mill and vessel (chrome steel, zirconia, tungsten carbide, etc.)

  • Hydraulic press and die (usually 40 mm)

  • Binding agents

Fused beads

  • Typical samples that are prepared as fused beads include rocks, cements, iron ores, etc. when higher accuracy is required.

  • Weighed sample is mixed with flux

  • Sample and flux are melted at ≈ 1000 oC

  • Melt is poured into a 40 mm mold

  • Bead surface needs to be homogenous (constant color without cracks)

  • Slow (10-15 minutes/sample)

  • High cost

  • Important benefit is that particle size problems disappear (fusion process results in a homogeneous glass)

  • An additional benefit is that the melting flux (usually Na or Li borate) dilutes the sample, reducing matrix variations, resulting in higher accuracy

  • Disadvantage –reduced sensitivity for trace elements

    Preparation equipment includes:

  • Fusion device (manual or automatic)

  • Pt/Au crucible(s) & mould(s)

  • Fusion (melting) flux

  • A non wetting agent (e.g. KI or LiBr) is sometimes used to help produce a better quality bead and to assist with cleaning the Pt/Au crucible & mould between samples


  • Typical samples include environmental (waters, mud) & oils

  • Easiest to prepare

  • Should have a constant volume that exceeds maximum penetration depth

  • Sample is poured into a liquid cell fitted with a thin plastic window

  • Range of window materials to suit different liquids

  • Fill to a constant height (e.g. 20 mm) to avoid errors from variable depth

  • Choose the correct thickness and material to suit the chemistry of the sample being measured

  • Na is lightest element that can be detected in liquids.

Influence of sample preparation

Factor of errors in Sample Preparation

Grain size and surface roughness

Uniformity of sample

Contamination through the sample preparation

Grain size and surface roughness

Uniformity of sample

Sand molding

Metallic Sample

Metal molding

Casting condition of the sample in the molding.

X-ray intensities differ according to the molding method which comes

In the measurement of light elements.

Quenching casting which makes the metallic composition fine produces good results

Sample polishing

Uniformity of sample

Contamination during polishing

As the contamination form the polishing belt to the sample, the re contamination from

The material of the polishing belt and from the remaining trace elements of polished


Contamination effect when carbon steel and Ni-Cr alloy polish after

polishing stainless steel.

Powder Sample

Grinding Condition

Different grinding condition cause variation in particle size distribution which

leads to variation in X-Ray intensity.

Powder Sample


Contamination from the grinding mill and media


Usual forming pressure – 20 tons with 40mm diameter.

X-Ray intensities varies with variation of forming pressure (especially

when pressure is low).



If you are given with four bottles of white powder. What will you do to identify them?

CaO,CaCO3,CaMg(CO3)2 Ca(OH)2 etc.

What is X-ray diffraction?

  • non-destructive analytical technique for identification and quantitative determination of the various crystalline forms, known as ‘phases’.

  • Identification is achieved by comparing the X-ray diffraction pattern

Diffractograms and ICDD Card

What is X-ray diffraction?

XRD able to determine :

  • Which phases are present?

  • At what concentration levels?

  • What are the amorphous content of the sample?

How does XRD Works???

  • Every crystalline substance produce its own XRD pattern, which because it is dependent on the internal structure, is characteristic of that substance.

  • The XRD pattern is often spoken as the “FINGERPRINT” of a mineral or a crystalline substance, because it differs from pattern of every other mineral or crystalline substances.

Crystal lattice

A crystal lattice is a regular three-dimension distribution (cubic, tetragonal, etc.) of atoms in space. These are arrange so that they form a series of parallel planes separated from one another by a distance d, which varies according to the nature of the material. For any crystal planes exist in a number of different orientations- each with its own specific d-spacing

Fourteen (14) Bravais Lattice

How does it work?

  • Diffraction

    Bragg’s Law


    When a monochromatic x-ray beam with wavelength  is incident on the lattice planes in a crystal planes in a crystal at an angle , diffraction occurs only when the distance traveled by the rays reflected from successive planes differs by a complete number n of wavelengths.

How does it work?

In powder XRD method, a sample is ground to a powder (±10µm) in order to expose all possible orientations to the X-ray beam of the crystal values of , d and  for diffraction are achieved as follows:

  •  is kept constant by using filtered X- radiation that is approximately monochromatic. (See Table 1).

  • d may have value consistent with the crystal structure (See Figure 5).

  •  is the variable parameters, in terms of which the diffraction peaks are measured.

Table 1: Monochromatic X-ray filters

Basic Component Of XRD Machine

  • Therefore any XRD machine will consist of three basic component.

  • Monochromatic X-ray source ()

  • Sample-finely powdered or polished surface-may be rotated against the center – (goniometer).

  • Data collector- such as film, strip chart or magnetic medium/storage.

By varying the angle , the Bragg’s Law conditions are satisfied by different d-spacing in polycrystalline materials. Plotting the angular positions and intensities of the resultant diffraction peaks produces a pattern which is characterised of the sample

Table 1: Typical experimental XRD data

Design and Use of the Indexes for Manual Searching of the PDF

  • Three search methods are used in the indexes – i.e.

    • The alphabetical index;

    • The Hanawalt index

    • The Fink index.

The Alphabetical Index

The Alphabetical Index

Figure 3: Schematic search procedure when chemical information is known

Hanawalt Method

The Fink Method


X-Ray Fluorescence

is used to identify and measure the concentration of

elements in a sample

XRF instrumental parameters

  • x-ray tube kv

  • x-ray tube mA

  • primary beam filters

  • collimator masks

  • collimator

  • crystal

  • detector

  • path

user benefits of wavelength dispersive XRF

  • versatile

  • accurate

  • reproducible

  • fast

  • non destructive

XRF is versatile

  • element range is Be to U

    atomic numbers (Z) of 4 to 92

  • concentration range covers 0.1 ppm to 100 %

  • samples can be in the form of solids, liquids, powders or fragments

XRF is accurate

  • generally better than 1 % relative (i.e. 10% ± 0.1%)

  • accuracy is limited by calibration standards, sample preparation, sample matrix, sampling, instrumental errors & statistics

XRF is reproducible

  • generally within  0.1% relative

  • good reproducibility requires high quality mechanics, stable electronics and careful construction techniques

XRF is fast

  • counting times generally between 1 & 50 seconds for each element

  • semi-quant analysis of all matrix elements in 10 to 20 minutes

  • overnight un-attended operation

XRF is non-destructive

  • standards are permanent

  • measured samples can be stored and re-analysed at a later date

  • precious samples are not damaged

properties of x-rays

the following four slides list some of the more important properties of x-rays that contribute to the nature of XRF analysis

XRF analytical envelope

the following section describes the five major areas that define the analytical possibilities available with wavelength dispersive XRF spectrometers

XRF analytical envelope

  • elemental range

  • detection limits

  • analysis times

  • accuracy

  • reproducibility

elemental range

  • beryllium (4) to uranium (92) in solids

  • fluorine (9) to uranium (92) in liquids

range of elements in solid samples are shown in green (Be to U)

range of elements in liquid samples are shown in green (Na to U)

detection limits (LLD)

  • function of atomic number (Z) & the mix of elements within the sample (sample matrix)

  • < 1 ppm for high Z in a light matrix (e.g. Pb in petrol)

  • or > 10 ppm for low Z in a heavy matrix (Na in slag)

XRF applications summary

  • Na to U in all sample types

  • Be to U in solid samples

  • accuracy generally 0.1 to 1 % relative

  • reproducibility typically < 0.5% relative

  • typical LLD is normally 1 - 10 ppm (depends on element being measured and the sample matrix)

XRF errors

the following section describes major source of errors in XRF analysis, and investigates how these errors can be minimized to achieve maximize accuracy

overview of XRF methodology

good accuracy requires

  • careful sample preparation

  • fused beads for light elements

  • accurate standards

  • selection of optimum instrument parameters

  • collection of enough counts to avoid statistical errors

Methods of Analysis

the following presentation describes the requirements for quantitative and semi-quantitative analysis

overview of XRF methodology

  • the objective of XRF is to determine as accurately as possible the composition of unknown samples

  • measured x-ray line intensities are converted to concentrations using an appropriate algorithm

overview of XRF methodology

each specific application needs to be looked at in detail to determine which method will be the most appropriate

XRF analytical methods

the atomic number (Z) of each of the elements to be determined will have

an influence on the type of sample preparation to be used, and the quantitative or semi-quantitative method that will be the most suitable

XRF analytical methods

  • the quantitative method is the most accurate, but requires calibration standards

  • semi-quantitative method is less accurate, but does not require standards

overview of XRF methodology

first determine the following:

  • which elements are to be measured

  • what are their concentration ranges

  • what accuracy is required

  • how many samples are to be measured

  • are suitable standards available

overview of XRF methodology

elements to be measured

  • low Z will require careful preparation

  • low Z may have lower accuracy

  • low Z may require fusion of powders

  • semi-quant does not measure the very light elements (Be to N)

overview of XRF methodology

concentration ranges

  • as the concentration range for each element increased, accuracy generally decreases

  • large concentration ranges will require more standards

overview of XRF methodology

good accuracy requires

  • careful sample preparation

  • fusion of powder samples for Z  13

  • longer analysis time

  • accurate calibration standards

  • careful selection of each variable instrument parameter

overview of XRF methodology

calibration standards

  • require the same sample preparation as unknown samples

  • accurate chemical analysis

  • need to cover concentration ranges

  • mechanically stable

XRF applications summary

  • Na to U in all sample types

  • Be to U in solid samples

  • accuracy typically 0.1 to 1 % relative

  • typical LLD is between 1 - 10 ppm

semi-quant (standardless analysis)

accuracy is limited by

  • particle size

  • inhomogeneity

  • non-measured elements (H to N)

semi-quant (standardless analysis)

accuracy of the semi-quantitative method can be as good as 1% relative; typically accuracy is between 5% and 10%

quantitative analysis

  • calibration graph (x-ray intensity v/s % element) is established for each element that is to be measured

  • measure unknowns using the established calibrations

quantitative analysis - calibration

for a single element (a), the concentration C is a function f of the intensity I

Ca = fa x Ia

quantitative analysis - calibration

for multiple elements (a & b) in a sample matrix, the concentration is related to both a & b:

Ca = f(Ia,Ib) or Ca = f(Ia, Cb)

quantitative analysis - calibration

the object is to obtain the best fit of experimental data to a given algorithm

e.g. method of least squares fitting

Σ(Cchem – Ccalculated)2 = minimum

where Σ = sum from all standards

and C = concentration

quantitative analysis - calibration

XRF software typically includes several quantitative methods. The most simplistic method is a straight line calibration where matrix (or inter-element) effects are absent

Soalan Pramakmal

  • Nyatakan 5 punca kesalahan analitikal analisis X-Ray.

  • Takrifkan sampel.

  • Apakah punca prosedur pensampelan yang lemah?

  • Nyatakan 5 perkara yang mempengaruhi kualiti penyediaan sampel yang ideal.

  • Terangkan prinsip kerja XRD.

  • Terangkan prinsip kerja XRF.

  • Berikan 5 contoh kaedah pensampelan.

  • Terangkan cara penyediaan “fuse beads”.

  • Nyatakan faktor kesilapan dalam penyediaan sampel yang mempegaruhi analisis X-Ray.

  • Apakah maklumat yang boleh diperolehi daripada keputusan XRD.

  • Tuliskan persamaan Bragg.

  • Nyatakan komponen asas dalam mesin XRD.

Soalan Pramakmal

  • Nyatakan 3 kaedah pencarian index unsur dengan manual PDF.

  • Apakah perbezaan kaedah Hanawalt dan Fink?

  • Lakarkan carta alir kaedah Fink.

  • Lakarkan carta alir kaedah Hanawalt.

  • Nyatakan julat no. atom yang boleh dikesan dengan kaedah XRF pada sampel pepejal dan cecair.

  • Apakah kaedah penyediaan sampel yang baik untuk unsur yang mempunyai no. atom yang rendah.

  • Kejituan keputusan XRF dipengaruhi oleh 3 faktor. Nyatakan fator-faktor itu.

  • Apakah itu LOI?

  • Login