Sample Preparation for XRF

Topics

• Sample prep is critical so will spend a lot of

time on this subject.
1. Introduction and key steps
2. Presentation to the XRF
3. Pressed Pellets
4. Fused Beads
5. Automated Sample Preparation
Typical Sample types presented for
analysis
 The Quality of the analytical
results obtained, in the first
instance is dependent on the
Quality of sample preparation.
 Sample Preparation

• This means that all the manipulations in the

preparation of a sample from its initial taking, to its
final submission to the instrument for analysis, must
be undertaken in an ordered and systematic manner.

• The first objective must be to derive an aliquot of

sample that is fully representative of the initial bulk
sample so that once prepared and analysed the
analytical results can be confidently reported as a
true reflection of the composition of original bulk.
Sample Preparation Aim
Sample Preparation Involves
• Sample Taking -- this produces the initial Bulk sample.
• Manipulation to reduce this Bulk to manageable size while
maintaining the Integrity of sample.
• Primary Preparation of the Bulk Sample. Jaw crusher, Pulverizer.
• Sample Splitting (Systematic reduction from Bulk to Specimen)
• One specimen to be used for XRF. Remainder for other techniques
or re-analysis. This remainder stored separately from original.
• Preparation of specimen as either a pressed powder pellet or
fused glass bead for XRF analysis
 Sample Preparation -
Primary Sample Taking
• Analysts are not always involved, but it is useful to know how and
where bulk samples were taken.
• Geological samples include Drill cores, Rocks, Soil/Sand samples,
Stream sediments, Minerals.
• Geologists will take or derive these samples according to a pre
determined plan dependent on their objectives.
• Production Control Samples are usually taken using an automatic
sample cutter on a conveyor belt. Examples are Raw materials and
Finished Product. Cement, Alumina, Iron Ore, Mineral Sands.
• Generally none of these samples are suitable and are also too
large for direct preparation for analysis.
Sample Preparation - primary Sample Taking

• Drill Cores will be sawn in half with Diamond saw. One half
stored and the other half put through a jaw crusher to produce
chips.
• Rocks will be put through a jaw crusher to produce chips. Chip
size typically 2 - 5 mm with modern jaw crusher equipment.
• Soil samples and Stream sediments are usually dried and
screened in the field camp and – 80 mesh sample sent to lab.
• There may be a need for analytical lab to also do screening on
Soil/Stream samples if geologist wants to establish which
fraction contains metals of interest. Manual and Mechanized
equipment available for this purpose.
 Sample Preparation - Sample
Splitting & Fine Grinding
• There are a variety of procedures involved in reducing these Bulk Samples
to an Analytical size Sample .
• Jaw crusher.
• Nested Sieving.
• Riffle Splitter.
• Primary Grinding mill - select mill vessel to avoid contamination. Very
important to decide what contamination is acceptable.
• Large Mill vessels available to handle large sample. No need to crush and
split. Can handle jaw crushed samples.
• Cone and Quartering to derive the Analytical size sample.
• Rotary Splitter to derive the Analytical size sample.
 Sample Preparation - Jaw Crusher

• Usually the first

step is jaw
crushing. Manual
or Automatic
CM20 Jaw Crusher reduces Rocks, Ore
and Drill core to less than 2mm mm
fragments

Automated Crushing is increasingly common

 Sample Preparation - Sieving

• Nested Automatic Sieve Shaker for

separation of dry soil/stream
sediment sample into different size
fractions.

• Possible contamination of samples by

mesh material.

• Typically Cu and Zn from brass.

• Fe, Cr, Ni from Stainless steel
 Sample Preparation
Riffle Splitter

• Used with the material

from the jaw crusher.

• Aperture width of
chutes match size of
sample fragments.

• Used to reduce the

mass of sample to a
suitable size for putting
through a milling
machine.
I prefer an Rotary Sample Divider (RSD), or an automated linear splitter
 Sample Preparation - Cone &
Quartering
• Can be used for
a large portion
of sample or in
the laboratory
after fine
grinding.
• Used at OT in
the concentrate
testing Lab –
would rather
use a RSD
 Sample Preparation
Rotary Splitter

• Used to split the finely

ground sample into
aliquots for analysis by a
range of analytical
procedures.

• Ensures that each aliquot is

a true representative of the
original bulk.

• This is the split that will be

used to prepare the XRF
specimen.

• All different sizes available

Sample Preparation
Pulverizing
• Pulverizing
– Manual – various sizes
– Automatic
– Programmable (time)
– Type of grinding vessels:
• Steel
• Tungsten carbide
• Agate
• Zirconia
Sample Preparation
Pulverizing

• Able to handle larger

samples which results in
obtaining a more
representative sample.
Especially suited to coarse
grained rocks.
• Large Ring Mills capable of
handling up to 5kg of
samples are available.
• Can be automated
 Sample Preparation - Possible
Contamination
• During these manipulations the samples will be subject to possible
contamination. Important to know which elements are to be determined to
avoid contamination.
• Jaw crusher plates contribute Fe, Mn, Cr, Ni and Mo.
• Milling vessels are available in a wide range of materials.
• Steel vessels contribute Fe, Mn, Cr, Ni, Mo.
• Tungsten Carbide vessels add W and Co.
• Carbon Steel vessels adds Fe and small amount Carbon.
• Agate vessel add Si but are very expensive and delicate (Special Applications
only when Ultra trace elements are to be determined)
• Zirconia vessels are extremely hard but add Zr and Hf.
Preparation of Samples
for
Analysis
by
XRF instrumentation
Preparation for Analysis
by XRF
• The prepared
specimen will be
mounted in a specimen
holder in order that it
can be placed into the
XRF spectrometer.
• This means that the
specimen must comply
with certain physical
requirements.
Specimen placement
in Specimen Holder
 Preparation of Specimen
by XRF
• The prepared specimen must comply with some physical
conditions:-
• These conditions are applicable to pellets and beads.
• Must have a flat surface for analysis. Distance to detector
compromised.
• Must be infinitely thick for the x-ray wavelengths to be
measured. Differs with matrix of sample.
• Must have a consistent thickness.
• Must be homogenous.
• Must be stable under vacuum. Powders in Helium.
 Preparation

of

Pressed Powder Pellets

 Preparation of Pressed
Powder Pellet
Briquet method

Crush, grind Apply pressure

and mix To standard holder
To grain Press
size <90um
Weigh out
Die
Protective ring

Mortar or crusher Specimen

9499D00400
 Preparation of
Pressed Powder Pellet

To prepare a pressed powder pellet we need to

determine-:
1. Optimal milling time to minimize particle size
effects.
2. The need to add a grinding agent.
3. The need to add a binding agent and the dilution
ratio.
4. Optimal pelletising pressure to produce stable
pellet
5. The need for backing material, aluminium cup or
steel ring
 Preparation of Pressed Powder Pellet

• At each step in the investigation the procedure must be capable of

the preparation of reproducible specimens. We should prepare at
least 5 specimens from same sample and determine standard
deviation using measured Intensities.

• Investigate a wide compositional range of samples to ensure that

specimen preparation method is capable of preparing comparable
pellets across this range.

• Need to be aware that Automated Prep equipment has resulted in

significant improvements in precision of specimen preparation.
 Pressed Powder Pellet
Particle size

• Important to have particles as fine as possible. At least 95% less

than 45 microns. Do screening tests to determine size achieved.
• We are trying to minimize particle size effects.
• Mineralogical effects remain. More later.
• Particle size achieved by milling will depend on sample
composition, mill vessel and milling time. Samples containing silica
will usually grind fine more easily.
 Preparation of Pressed Pellet
- Particle size
• As samples must also be homogeneous milling will usually ensure this
is achieved. Exception - agglomeration.
• Pellets must have a mirror like flat surface. This is important for long
wavelength radiation e.g Na and Mg (lighter elements). Coarse
particles will not be capable of producing this finish.
• A polished die surface is also required to achieve this finish.
• Once we have achieved a satisfactory particle size we need to see if
material will form a pellet.
 Preparation of Pressed Pellet
Particle size
• Composition of milling vessel will also influence grinding time.

• WC vessel being denser will be capable of finer grind in shorter

time. BUT Capable of contamination with W and Co.

• Particle size achieved will also depend on grinding time.

• We need to match milling vessel with sample, analytical

requirements and time available for sample preparation.
Preparation of Pressed Pellet
- Particle size effects

• Coarse

• Fine
Optimization of Milling Time

25

20

15
Mg
Int
Al
10
Si

0
10 secs 20 secs 30 secs 40 secs 50 secs 60 secs
 Preparation of Pressed Pellet
- Grinding Aids
• Some specimens will agglomerate or cake during grinding and
further particle size reduction will be inhibited.
• Slurry grinding is one way of getting around this problem as
particles remain in suspension and cannot cake.
• Commonly used liquids are Alcohol, Propylene glycol, Acetone.
• It is a messy business and time consuming as liquid must evaporate
in fume hood. Beware also of dangerous reactions.
• Dry grinding is preferred and experimentation is necessary to
match grinding agent with specimen .
Preparation of Pressed Pellet
- Mineralogical effects

• Silica particle

• Silicate
particle
 Preparation of Pressed Pellet
- Mineralogical effects

Pressed pellet sample preparation is not

normally recommended for applications where
there is chance of “mineralogical effects”
occurring. This will occur when a major element
is present in two or more minerals of different
composition. In your situation Ca is available in
Dolomite and limestone. Cu is available in
Malachite, Chalcocite, Chalcopyrite, Cuprite and
Azurite
Preparation of Pressed Pellet
- Mineralogical effects

• Mineralogical effects can only be eliminated by fusion

where we in fact destroy the crystalline structure of the
component minerals which contain the elements we are
trying to determine.

• We deal with fusions in a later presentation.

 Preparation of Pressed Pellet
- Binding agent
• Samples which contain a mixture of soft and hard components will
usually pelletize quite easily without addition of a binder.
• If sample components are essentially hard, i.e. high silica content they
will not form a coherent pellet easily because the grains are angular and
will not stick together without some assistance.
• Addition of binding agent will be essential in this case.
• Choice of binding agent depends on elements to be determined as do
not want to add any analyte elements to specimen.
• Proportion of Binder to be added should be as small as possible to avoid
undue dilution but still able to produce an acceptable pellet which will
not disintegrate under vacuum.
Preparation of Pressed Powder Pellet
- Function of Binding Agent

• Specimen
fragments

• Binder
 Preparation of Pressed Pellet
-Binding agent
• Do the samples need addition of Binding Agent to form robust pellet.
Automated sample loading of unmounted pellets can damage pellet.
and/or
• Pressed powders can introduce dust into the spectrometer chamber
with unfavourable consequences.

• Residue left behind in sample cup between samples can influence

distance to tube and detector and consequently the results. Clean
everything well!
 Preparation of Pressed
Pellet - Binding agent
• Binders can be liquids or powders and range from commonly
available reagents to brand names with secret formulas.
• The objective with addition of a binder should be to produce a
stable, crumble-proof sample pellet with minimum of dilution,
contamination and effort.
• Commonly used binders include Cellulose, Wax, Wax/Polymer
blend, Boric Acid, Paraffin, Mowiol binder.
• The binder acts as a type of glue, being squeezed into interstitial
spaces between the grains and cementing them together.
Preparation of Pressed Pellet - Binding agent

• Selection of most suitable binder for your specimens will depend

on the following considerations:
• Ability to produce robust and stable pellet.
• Easy removal of milled specimen powder from mill vessel.
• Easy cleaning of mill vessel after removal of powder.
• No moisture pickup by pellet during storage as pellet will swell up
and crack. Wax binders are good in this respect.
• Is it a lubricant for the die.
• Some Binding agents can also act as grinding aid.
• Usually added at 10% by weight. Determine experimentally.
Grinding/Binding Aids for
Preparation Pressed Pellet

• Grinding and Binding

aids available from
Several suppliers
including IMP.

• Cellulose
• Paraffin binder
• Propylene Glycol
 Preparation of Pressed Pellet
- Briquetting Pressure
• Determination of pelletization
pressure is important.
• It is possible to pelletize at low
pressure ( 5-10 tons/sq inch) and
produce a stable pellet. This is
usually possible only with sample
which have soft components .
E.g. - Cement, Clays.
• Also possible if particles are <-
300 mesh (45 um)
• It is better if we can pelletize
without binder as we do not Automatic Mill and Pellet Press
contaminate sample.
 Preparation of Pressed Pellet
- Briquetting Time
• Determination of holding time at pressure is important.
• This permits binding agents to glue the particles together into a
coherent mass.
• Determine optimal pressure and holding time to produce a stable and
reproducible pellet across the compositional range of standards and
unknowns.
• Optimal grinding time, grinding aid, binder, pressure and time are all
determined empirically (experimenting).
 Pressed Powder Pellet
- Problem

• Sample high in silica.

• Too little binder

added.

• Too high pressure.

• Can disintegrate under

vacuum.
Optimization of Pelletising
Pressure

25

20

15
Mg
Int
Al
10
Si

0
2 tons 5 tons 10 tons 15 tons 20 tons

Stabilizing of intensity shows we have optimum pressure at 15tons

 Preparation of Pressed Pellet
- Boric Acid , Aluminium Cup, Steel Ring

• Once we have established pelletization procedure is briquette robust

enough for handling or is there a need for support.
• Pelletization into an aluminium cup provides a very strong support for
the specimen. Is suggested especially for calibration standards which
will undergo repeated handling.
• Unknown specimens may also require a support to give them added
strength for handling.
• Automated sample preparation systems where samples are handled
by robotic arms usually employ re-usable steel rings.
• Geological samples are often pressed onto a boric acid backing to give
additional strength to the pellet.
Various Backing Options

• Steel Rings

• Sample rings

• Aluminium
Cup
Preparation of Sample with
Boric acid backing

• Layer of sample
pressed onto boric
acid backing.
• Sample pellet is
robust for handling
• XRFs don’t like boric
acid!
• Hazardous Substance
so care require.
• Not often used in
commercial
environments
Preparation of Pressed Pellet with
Boric Acid Backing

• Die Sleeve and Plunger

Set for preparing a
specimen with backing
such as Boric Acid.

• Pressed powder pellet.

Preparation of Powders as
Pressed Pellet
• Die Set with
plunger,
polished
steel pellets
and knock
out ring for
specimen
pellet
extraction.
Preparation of Powders as
Pressed Pellet

• Aluminium
cup for
preparation
of pressed
powder
pellet.
Preparation

of

Fused Glass Beads

Preparation of Glass Beads

Melting method

Heat for
Weigh out Cast & Cool
Melting
and mix

Flux + Specimen 1000° -1100° C

To standard holder
Glass disk
specimen
Platinum crucible Remove bubbles
9499D00500
Preparation of Glass Beads
• Preparation of powder as fused glass bead
involves weighing out sample and flux, placing in
Gold/Platinum crucible, heating to 1000 – 1200
degrees and casting as a flat glass bead by pouring
melt into a heated Gold/Platinum mould and
cooling under controlled conditions.
• Manual or Automation
• Depending on nature of sample – PRE oxidation
may be necessary.
Preparation of Glass Beads

• Particle size and mineralogical effects are removed or diminished

by fusion of the sample with a suitable flux to form a glass bead.
• Synthetic calibration standards can be made by mixing pure oxides
at concentration levels to suit the analytical range.
• Depending on sample type, fusion can even be quicker than
pressed powder procedure.
• Generally accuracies and reproducibility are superior with fusion
procedure.
• Only drawback is possible dilution of trace elements and therefore
inferior LLD. Low dilution fusions are possible
• More expensive than pressed powders
 Glass Beads – Key Points

• To prepare a fused glass bead with our

representative specimen we need to determine:-

• Need for oxidation.

• Optimal fusion mixture.
• Optimal fusion temperature.
• Optimal fusion time.
• Need for Non Wetting/Releasing Agent.
 Preparation of Glass Beads
• Samples must be fine for complete dissolution in flux mixture, usually around
100microns.
• Oxidation state of sample components is important.
• Addition of Oxidizing agent may be necessary to prevent damage to crucible, for
retention of S and better dissolution of sample.
• Composition of flux mixtures is important. Agitation during fusion facilitates
homogeneity of glass.
• Fusion temperature is important to ensure complete dissolution.
• Addition of non wetting agent may be necessary to ensure all melt leaves the crucible
and the bead is released from the mould.
• Cooling after fusion is important to prevent bead from shattering or crystallizing.
• Need to be aware that peroxidation may be required. PRE oxidation is essential if the
sample contains reduced species such as organics, metallics (Fe, Cr, Cu, Pb, Zn and their
alloys)
Particle size of Sample Powder
Fused Glass Beads

• Samples must be as fine as possible for efficient dissolution

during fusion. Desired size < 100 microns.
• The grain size of sample and flux should be similar as this will
facilitate mixing and homogeneity during fusion.
• The most common problem with non homogeneity during fusion
is the presence of large individual sample particles. - Especially
Refractory minerals such as Zircon, Quartz, Ilmenite, which are
hard and require vigorous grinding.
• When checking homogeneity of your glass beads by measurement
- if you are having trouble achieving good reproducibility go back
and check grain size consistency first.
 Loss On Ignition of Sample
Fused Glass Beads
• Oxidation by independent heating
results in a LOI or TGA.
• Samples which contain carbonates and
other volatiles can be ignited to 1000o
Celsius in a muffle furnace to determine
Loss On Ignition.
• Compensation for LOI needs to be made
during data processing.
• Instrument software can also calculate
LOI on Un-ignited samples. Must be sure
all elements present are accounted for
as LOI is calculated by difference and
used in compensation calcs.
 Fluxes for Preparation of
Fused Glass Beads
• Composition of flux/flux mixtures is important.
• Choice of Flux mixture depends on composition of
samples.
• There are two classifications of Sample either “Acidic” or
“Basic”
• “Acidic” samples are high in Si, Al, Fe, S oxides.
• “Basic” samples are high in Ca, Mg, K and Na oxides.
• Fluxes are classified on their ability to to react with these
oxides.
• Lithium tetraborate reacts with “Basic” oxides i.e. CaO,
MgO, K2O, Na2O. Optimal for cement.
• Lithium metaborate reacts with “Acidic oxides i.e. SiO2,
Al2O3,Fe2O3.
• May need a non-wetting agent - may be necessary to
ensure that no material remains in the crucible during
casting procedure
Fusion Temperature for of
Fused Beads
• Fusion temperature is important to ensure complete dissolution.
• When having trouble with dissolution avoid just ramping up the
temp to solve the problem.
• Try different flux mixtures first. Ratio of LiT and LiM.
• Try some additives such as LiF, Li2CO3. Beware of bubbling with
carbonate additives as a result of the expulsion of CO2.
• Cross contamination of samples can result if working in confined
space such as a muffle furnace.
Agitation in the Preparation of
Fused Glass Beads
• It is essential that the fusion melt
once in a liquid form is subjected to
some form of agitation.
• If employing a completely manual
procedure (Heating in muffle furnace
) the crucibles must be manually
swirled during the process.
• Most fusion machines today
incorporate an agitation mechanism
of some kind during fusion.
Fusion Equipment
Auto Fusion & TGA/LOI
Cooling in the Preparation of
Fused Glass Beads
• Cooling after fusion is important to prevent bead from
shattering.
• The rate of cooling after casting the molten glass into the mould
will determine the durability of the glass bead.
• Usual procedure is to allow bead to cool down without air draft
until red heat has disappeared.
• Fans may then be activated to continue cooling process.
• Once cool enough the bead can be removed from the mould and
placed on clean dry surface to reach room temperature.
• Label bead immediately with sticky label with unique sample ID.
 Handling
Fused Glass Beads

• Handling and storage of glass beads is important.

• Avoid touching analytical surface with sweaty fingers. Sodium
contamination is very easy. Wear gloves
• Store glass beads in plastic bags and preferably in a desiccator or
special desiccated cabinet.
• Clean analytical surface with alcohol if necessary.
• Take particular care when handling and storing calibration
standards
 Care of Platinum Ware

• Platinum/Au crucibles and

moulds are expensive items.
• They must be treated with care
and looked after.
• If you have sample residue in
the crucible don’t try and
remove it physically i.e. with
sharp objects . Scratches inside
crucible will cause retention of
fused material.
• Clean crucibles and moulds in
Ultrasonic bath with Citric acid.
The Good, The Bad & The Ugly

Crystallization
Good

Insufficient material/ Stress

Too low fusion temp
 Fused Beads
How they Should Look!!

• Fused beads

• Platinum crucibles

• Platinum moulds

• How they should look to

produce good beads.
 Some typical Problems with Glass Beads

• Insufficient heating and undissolved material

• Temp of casting mould too low
• Incorrect choice of flux
• Handling of bead when not at ambient temperature
• Dust or remnant material in casting dish
• Forced cooling too early/Airflow too strong
• Fusion temperature too low or fusion time too short.
Increase.
• Sample particles too large. Increase grinding time.
 Some typical Problems with Glass Beads

• Sample and flux not mixed properly before fusion.

• Sample – flux ratio too low. Add more flux.
• Sample contains non oxidized component. Either add oxidizing agent
to fusion mixture or pre-oxidize sample by heating in muffle furnace.
• Non homogenous dissolution.
• Undissolved particles because powder not fine enough.
• Increase swirling speed and time of fusion.
• Increase flux ratio.
• Use a different flux composition i.e. more acidic or more basic
• Plus many more!!!
• Automation will standardize and solve these issues
Automated Sample Preparation
Traditional Sample Prep
It’s horrible work 
 Automation of the Sample
Preparation Procedure

Automation of the sample preparation

procedure although expensive has some real
benefits.
• The most significant is the big improvement
in Reproducibility
and Accuracy
• Robotic manipulation of samples from
arrival at lab to analysis are not subject to
human errors.
• More samples are produced with less people
so productivity increases
• Costs are lower per sample and costs are
managed
• Major improvements in Health and Safety
 Laboratory Automation

Sample Sample Analysis

Transport Transport
Collection preparation

• Slurry • Dry
• • Crush • XRF
Dry
• • Split • XRD
Large
Primary • ICP-MS
• Small • Pulverise
Crush & • Etc
• Press
Split
• Fusion
• Digestion / Wet Chemistry

SAMPLE is TRACKED and MANAGED in PrepMaster and/or LIMS

Automated Lab Concepts

• IMP Automated labs are

custom designed to suit your
requirements
• Robotic or linear or modular
compact systems are available
• All industries – Mining,
Cement, Aluminium - wet and
dry analytical procedures
 Laboratory Automation
Concepts

Robotized Automation Concept

Linear Automation Concept

 Laboratory Automation Concepts
4 1
3

8 Typical
8 Components of
6 the slurry
2 automation
5

1 3 5 7
Automatic filter unit Cakebreaker unit HP-M XRF or XRD
Mixer/ filter press Crusher/ splitter Pulverizing mill analyser

2 4 6
Microwave oven Magazine HP-P 8
Composite samples Pelletizing press Industrial robot
Laboratory Automation Concepts

• Sample
receiving
station
• Automatic
splitting
• Automatic
milling
• Automatic
pelletization
• Automatic drift
correction.
NJV Manual x Automated Preparation

Slide 80
The case for automation - Safety

 Reduction of operators interacting with equipment, eg handling of materials, handling of

hot materials (fused glass beads)

• Prior to the introduction of the automated laboratory the highest frequency injury in the
manual lab was burns due to the automated bead casters.

 There are also other safety risks that are reduced

• Lowered exposure to dust

• Lowered exposure to noise

• Lowered manual handling risks

Manual Handling

 In the manual based laboratory each sample could be handled up to six times in its full
sample mass before being processed. Typically the process below was followed

• Sample pick up
• Sample drop off
• Sample riffled
• Sample crushed
• Sample loaded onto oven trolley
• Sample removed from oven trolley
• Sample pulverised
• Sample weighed out for analysis

For every movement the risk of incurring

a manual handling injury increased.
There was also the risk around highly
repetitive tasks
Inhalable dust exposure

Slide 83
 Noise exposure

Noise

90

88

86

84
Noise level (dB(A))

82
New lab
80
Old lab
78

76

74

72

70
1 2 3 4 5 6 7 8
Tests
Data collected when original mill design in use. Subsequent upgrade has further reduced noise output

Slide 84
 Conclusion

The best XRF in the world is useless without the right sample
preparation!
• Be consistent in your method
• Experiment with the sample preparation techniques to determine the
best method for your application
• Fused Bead Method is normally more complex and expensive then
pressed powders BUT solve matrix issues. Need to consider oxidation,
Optimal fusion mixture, Optimal fusion temperature and Optimal
fusion time.
• pressed powders MUST be made well!
• When making pressed powders particle size is critical
• Pressed powders may not work for geological samples because of
mineralogical effects
• Automation is proven to provide more repeatable and accurate results
Experiment first then stick with your method!