XRD – What Is It & How Can It Help You?
X-Ray Diffraction (XRD) is a technique for examining the arrangement of atoms in a crystal lattice. This is a comparative technique where the pattern obtained for a sample is compared against standards collected over the hundred year history of the technique. Elemental composition is not determined by this technique but can be inferred from the results. Confidence in matching the phases can vary depending on how closely the database pattern matches the fraction present in the sample, the number and type of other phases present in the sample, crystallinity, concentration of the phase and the quality of the XRD trace.

Other information that can be gleaned from an XRD trace includes the degree of weathering or alteration, crystallite size, substitution, degree of disorder and the amorphous content.

In real world samples it is common to have over a dozen different crystal phases at varying concentrations in a complex sample. The use of elemental assay, information of the samples history and location and complimentary techniques all assist by strengthening confidence in making phase identification.

XRD techniques vary from qualitative to semi quantitative through to full Quantitative Rietveld analysis. Each technique will deliver different levels of accuracy and precision proportional to the amount of work required to improve accuracy through sample preparation, instrument running and analysis.

One of the most challenging areas for phase identification is clay speciation. Due to the poor crystallinity and irregular ordering of some clay groups, identification may require further work involving glycolation, heat and other techniques.

At Microanalysis we have several automated powder X-ray Diffractometers. We have a number of diffraction databases including the latest 2018 complete International Centre for Diffraction Database (ICDD). Our standard holders take approximately one cubic centimetre of powdered sample. We also have holders that take milligram quantities of sample, holders that can present filter cloth, flat ceramic or metallic plates and holders that can accommodate some sample irregularity.

The techniques we frequently utilise are:

  • Qualitative XRD where the phase identification is conducted and the minerals are classified as major, minor and trace.
  • Semi-quantitativein which the phase identification includes a concentration which is calculated using the normalized reference intensity ratio method where the intensity of the 100% peak divided by the published I/Ic value for each mineral phase is summed and the relative percentages of each phase calculated based on the relative contribution to the sum. An estimation of the amorphous content can also be given.
  • Spiked semi-quantitative which is similar to a standard semi quant with a higher confidence in the concentration values and the estimate of the amorphous content.
  • Quantitative XRD analysis using an internal standard, with Rietveld analysis to give the highest confidence possible in the concentration of phases and amorphous content determined.
  • Crystalline silica determinations for alpha quartz, cristobalite and tridymite. A full phase identification is performed to check for overlaps that may be present from phases present. A specific peak scan is then performed with this result compared against a five point calibration curve to produce a value of each crystalline silica phase present.
  • Clay speciation. A Semi-quantitative analysis is performed followed by gylcolation and heating to determine specific clay groups.
  • Respirable free silica determination. A semi-quantitative analysis is performed on the respirable fraction and is combined with particle size determination and is checked using scanning electron microscopy.
  • Comparative XRD. If there is no entry in the databases for the compound you examining but you’re have or can construct a suitable reference pattern standard, then this technique would still be of value to you.
  • Specific mineral semi-quantitative analysis. The phase(s) of interest are concentrated through solvent washing, heavy liquid separation, magnetic separation or other specific techniques to give better confidence in the identification or to enhance XRD features to study substitution.
Microanalysis is always pleased to customise XRD techniques to accommodation specific requirements and samples to achieve the highest quality results to meet the price point of the client.

Ian Davies – Analytical Scientist

When The Size Makes The Poison
You’ve heard the saying ‘the dose makes the poison’, and it’s true – the concentration of a toxic substance makes the difference between being at or below the ‘no observable effect concentration/level (NOEC or NOEL) and death. But concentration isn’t the only factor when you’re looking at certain hazardous materials.

Respirable crystalline silica (RCS), which is listed by the International Agency for Research on Cancer (IARC) as a Group 1 Carcinogen, is a known industrial and occupational hazard. But why? Crystalline silica (of which the most common form is quartz, the second most common terrestrial mineral) is all around us, in playground sand and rocks, and as an integral part of concrete and mortar. Yet we don’t see people dropping dead from silicosis every few meters, and most people have only been injured by quartz if they dropped a big rock on their foot or got sand in their eye at the beach.

That brings us to size. Quartz (and cristobalite and tridymite, the other two primary polymorphs of crystalline silica) is hazardous if it’s small enough to get deep into your lungs and get trapped. Silicosis is a devastating lung disease, which can take years to develop, caused by fine silica particles embedding themselves in the alveolar sacs and ducts where oxygen and carbon dioxide gases are exchanged. When our lung’s cleaning macrophages try to dispose of the nuisance dust, the toxicity of the crystalline silica causes an immune response that releases a bunch of nasty stuff, and this results in characteristic fibrous nodules and scarring (plaques) in the lungs.

So – how small is small enough to cause lung damage? The usual nomenclature for airborne or potentially airborne particulate size is the Particulate Matter (PMx) parameter. The PMx values of interest are the ‘respirables’ PM2.5 and PM4 (2.5 is used in the USA and 4 is used in Australia – this size gets all the way down into your lungs), PM10 (Thoracic – it’ll get caught deep in your throat or in the top of your lungs and will probably be coughed out in mucous), and PM100 (inhalable – will just stick in your mouth or the top of your throat and will likely be coughed or spat out, or swallowed). The value after PM is referred to as the ‘Equivalent Aerodynamic Diameter’ or EAD and shouldn’t be confused with physical diameters.

There are several different types of physical diameter that can be measured:

·         Average diameter is measured by laser diffraction;
·         The second highest diameter is measured by sieving; and
·         The greatest diameter is measured by laser extinction.

All of these measured diameters cover the physical dimension of a particle, which is only one aspect that dictates how a particle will fly through the air and find its way into your lungs. The other factor that controls how long a particle floats around in the air is the density of the particle – the denser the particle, the heavier a particle of the same size will be, and the more likely it is for a particle to settle straight to the ground. So the higher the density of a material, the smaller the particle needs to be to get into the lungs. The EAD takes into account the density of the particle to model an equivalent particle with a density of 1 g/cc. For quartz, with a density of 2.65 g/cc, this is approximately 2.5 µm which is the equivalent of a water droplet with a diameter of 4 µm.

Apart from appropriate PPE (always wear your P2 mask!) and dust suppression measures, there are several ways that RCS can be monitored and controlled. In areas with likely exposure, personal and location air monitoring is used to monitor the levels of airborne dust. Either FTIR or XRD can be used to determine the concentration of RCS on the filters and this can be equated to a mass per unit volume, and compared to the relevant industry TWA limits.

When predicting whether a material is likely to release hazardous levels of RCS, it is important to determine both the size distribution and the proportion of the PM4 dust that is crystalline silica. This method is commonly called the Size Weighted Respirable Fraction (SWeRF) method. Another factor to take into account is the friability of the material, and whether it is likely to become finer during routine handling. If the material is likely to produce more fines due to its physical properties or the use for which it is intended then more RCS may be produced.

Using XRD, Microanalysis Australia can quantify the respirable fraction of crystalline silica (RFcs) to a detection limit of better than 0.0001 wt % in bulk materials and below 10 µg on an air monitoring filter membrane.

If you’d like to ask about respirable crystalline silica determination on air monitoring filters or bulk samples, feel free to give us a call!

Nimue Pendragon
Lead Consulting Scientist

Asbestos and Other Types of Fibres
A rose by any other name….
The difference between biosoluble and bioinsoluble fibrous minerals.
Image 1: Halotrichite
Image 2: Actinolite
We’ve all seen fibres – they are everywhere. Cotton strings off cloth, fibreglass, carbon fibre. But there’s one word that makes everyone jump to attention. Asbestos.
What’s actually the difference between asbestos and other types of fibre?Asbestos is incredibly useful – it is fine, flexible, strong, heat resistant; the perfect material for all applications. It was added to concrete, paint, rubber, metals – it was the wonder material. Except for the horrible carcinogenicity.

Epidemiologically, it soon* became very clear that known asbestos fibres like crocidolite (fibrous riebeckite) and amosite (fibrous grunerite) caused lung cancers including mesothelioma. Humans began to move away from using asbestos as a cure-all for material shortfalls.

Humans began to manufacture substitutes – slag wool, glass wool and refractory ceramic fibre were some of the first. Unfortunately, the closer to the other qualities of asbestos they came, the more likely that they were found to be hazardous in the same ways. So what properties of asbestos are so harmful?

As asbestos enters the lung, like any other dust, the depth to which it penetrates is dependent on the equivalent aerodynamic diameter. If the fibre is fine enough to get deep into the lung, the body can’t cough it out and has to use more complex disposal methods. The lungs have a self-cleaning mechanism called ‘alveolar macrophages’ which act like little mouths and enclose nuisance dusts that manage to make their way that far into the lung. The macrophages then immerse the dust in acidic fluid to dissolve it and carry the dissolved material out of the lung to be dealt with elsewhere.

With asbestos fibres, the diameter is small enough to enter the macrophage but the fibre is long enough that it can’t close its ‘mouth’. Because the fibre is not dissolved by the surrounding fluids (it is bioinsoluble), this prevents the macrophage from doing its job and removing the fibre and kills the macrophage in the process. This results in scarring and can eventually lead to mesothelioma and other lung cancers.

This relationship between the diameter:length aspect ratio and the ability of the fibre to kill macrophages is the reason that the fibre definitions for different industries are based on aspect ratio. The three main definitions of a countable asbestos fibre are:

  1. DMP (Department of Mines and Petroleum): < 1 µm diameter, > 5 µm length
  2. NOHSC: < 3 µm diameter, > 5 µm length, aspect ratio of > 3:1
  3. USEPA: > 10 µm length, aspect ration of > 3:1, substantially parallel sides

The other property of the fibres that is significant is the mineralogy, as some minerals are biosoluble (the surrounding lung fluid will dissolve the fibre anyway, even if it isn’t disposed of by the macrophage). Only the bioinsoluble minerals pose a health risk.

Only six different minerals are classified as asbestos. Chrysotile, Crocidolite (asbestiform Riebeckite), Amosite (asbestiform Grunerite), Actinolite, Tremolite and Anthophyllite (asbestiform Cummingtonite). All of these minerals were once sold commercially as asbestos, but they aren’t the only minerals with these properties. Later, it was discovered that other minerals with the same high aspect ratio and bioinsolubility caused the same kind of diseases. Some other hazardous fibres include Winchite, Richterite, and Erionite.

There are also a significant number of minerals that have the same morphology (high aspect ratio fibres) but don’t pose the same risk as the fibres simply dissolve. Some examples are Epsomite, Ettringite, Halotrichite and sometimes simple Halite, or table salt, can form similar fibres.

So how do you tell them apart? That’s where we come in.

Optical microscopy has historically been used for identifying fibrous materials. It’s quick, cheap and doesn’t require much sample preparation so it’s ideal for a quick check for fibres. However, it has some notable limitations:

  1. Optical miscroscopy has magnification limits which mean that very fine, highly toxic fibres (< 0.5µm in diameter) are unable to be detected;
  2. Optical microscopy can tell limited information about the mineralogy, so often can’t differentiate between biosoluble and bioinsoluble minerals; and
  3. Although Polarised Light Microscopy (PLM) can differentiate some types of asbestos using oils of specific optical properties, the technique can’t identify all types, and can’t identify other minerals, hazardous or otherwise.
Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray Spectroscopy (EDS) can take very high resolution, high magnification images that clearly depict very fine fibres. The EDS determines the elemental composition, which can pinpoint the mineralogy of the fibres and identify whether they fall into the hazardous, bioinsoluble category. In some cases, multiple minerals have very similar elemental composition, and X-ray Diffraction (XRD) can be used to confirm the mineral assignment.
* approximately 30 years laterNimue Pendragon

FTIR Microscopy

Speciating contaminants in everyday products, from food and beverages to crime scenes, from building materials to aviation fuel, understanding the composition of errant particles is key to determining the source and solving the reason they ended up in places they weren’t meant to be! Microanalysis Australia is keen to announce the addition of an FTIR microscope to it’s line of investigative equipment.

Our PerkinElmer Spectrum2 now has an accessory which allows enhanced spatial resolution to discriminate particles down to 20 µm in size against backgrounds which would otherwise swamp a typical ATR measurement. Multi-layer specimens such as paint films can now be analysed to determine polymer composition differences between coatings – matching paint flecks to potential sources and confirming proper application etc, to name a few. Microanalysis is routinely requested to filter solutions, from potable waters, to agrochemicals to look at known contaminants and determine possible sources. Whilst SEM/EDS has been an enormous help with these unknowns in the past, FTIR microscopy adds another string to the bow of being more absolute in pin-pointing the ultimate source of the tinniest of particles.

 

ACA and SCAA Laboratory Tour

On Wednesday 1st November, Microanalysis held a special information evening for the Australasian Corrosion Association (ACA) and Surface Coating Association Australia (SCAA) professional associations.

Pulling everyone away from the tasty nibbles and drinks, the 12 members had a guided tour of the Laboratory to learn a little of what Microanalysis Australia is up to in the corrosion field as well as in a diverse range of other industry sectors.

Exploring the lab, the delegates learned about spatial elemental  analysis in the two Zeiss SEM/EDS systems, identifying corrosion products versus naturally occuring ferrous phases in the two Philips/PANAlytical XRDs, sizing microbes in the Malvern Mastersizer, understanding settling rates using a Sedigraph, Hiac Royco Particle Counters for contaminat concentration determination in liquids – particularly important for corrosion inhibitor cleanliness and surface corrosion and pitting analysis on the  Solarius Laser Profilometer.

The group learned about the UNDG testing that Curtin University and Microanalysis have been involved in with regards the C1 ‘Localised Corrosion – Intrusion depth’ research. The Solarius Profilometer has been an invaluable tool in terms of scanning large corroded areas to obtain pit depth and profiles.

After the tour,  the group returned to the drinks and food where Nimue Pendragon and Owen Carpenter presented some information about failure analysis using SEM EDS, bulk goods testing by ADG and IMDG, and UNDG C1 corrosion analysis by laser profilometer. Download a copy of the presentation below.

We hope an informative evening was had by all.

  • NATA
  • Australian Institute of Petroleum
  • Australian X-Ray Analytical Association
  • Royal Australian Chemical Institute
  • Telstra Business Awards
  • Scientific Partners Australia