microanalysis

One Analysis Technique – So Many Options!

Roger Kerstin, North America Sales Manager, EDAX

X-ray Fluorescence (XRF) solutions – which type of XRF instrument should I choose?

Most of the XRF systems out there are very versatile and can be used in many different applications, but they are typically suited for a specific type of analysis. Since the discovery of XRF many decades ago there have been new developments and new instruments just about every year. The term Florescence is applied to phenomena in which the absorption of radiation of a specific energy results in the re-emission of radiation of a different energy. There are two different types of detectors for XRF systems: Wavelength Dispersive (WDS) and Energy Dispersive (EDS).

In energy dispersive analysis, the fluorescent X-rays emitted by the material sample are directed into a solid-state detector which produces a “continuous” distribution of pulses, the voltages of which are proportional to the incoming photon energies. This signal is processed by a multichannel analyzer (MCA) which produces an accumulating energy spectrum that can be processed to obtain analytical data.

In wavelength dispersive analysis, the fluorescent X-rays emitted by the material sample are directed into a diffraction grating monochromator. The diffraction grating used is usually a single crystal. By varying the angle of incidence and take-off on the crystal, a single X-ray wavelength can be selected. The wavelength, and therefore the energy, obtained is given by Bragg’s law:

nλ = 2d Sinθ

In the XRF world there are many different types of instruments to choose from: large systems to small systems; high powered systems to low powered systems, floor standing systems to benchtop to portable systems.

What do I choose, where do I start?

The answer to these questions is that it really depends on the samples you are trying to measure and the performance you are trying to achieve. I really classify these instruments in 3 different categories: bulk, portable, and small spot.

Bulk XRF: This typically means that you have samples that are either powders, liquids or even solids that you need to analyze quickly. Bulk instruments have a large x-ray spot size to excite a lot of the elements fast and get a quick answer. They can be EDS or WDS instruments, benchtop or floor standing, and low or high power. The kind of analyzer will determine what you can or cannot measure. The higher the power, the lighter the elements and the lower the concentrations. The benchtops typically are lower power (50kv and lower) and are usually decent for go/no go type analysis and even everyday type of analysis when super low LOD’s are not needed, or light elements (below Na) are not of a concern. If you need lighter elements or lower LOD’s then typically you would go with a high power WDS system and these typically can go up to 4kw of power and have a vacuum chamber or He environment .

Portable XRF: This is just what is says – portable. These analyzers are typically used for sorting metals, in the geological field, or anything that you can’t just bring to the lab. The performance of these have come a long way and they are a critical tool for many industries. They tend to have a larger spot size but since they are portable they must be light to carry around all day. They are typically lower power and lower current, which does not allow them to have the same type of performance as the lab type instruments but usually they are good for sorting and identifying samples. They are also very good for ancient artifacts or paintings that can’t be brought to a lab.

μXRF (Micro spot XRF): These are the instruments that have a small spot size compared to all other XRF systems and they are used in smaller sample identification or mapping of a sample. There are several different types of μXRF analyzers. Some use collimators to focus the beam (this typically loses intensity) for applications like coating thickness testing or alloy id. These are usually designed to be inexpensive and benchtop for quality control applications. They are versatile but also limited to the elements they can measure. Most of these only analyze down to Potassium as they usually do the analysis in an air environment. Then there are μXRF systems that use optics to focus the x-ray to smaller spot sizes. These are used for more in-depth analysis, and are equipped with a vacuum chamber, mapping and low LODs.

Before buying an XRF system many factors must be taken into consideration and you need to ask yourself some of the following questions to really determine the best fit for your applications.

• How big is my sample?
• Can I destroy my sample?
• What levels of detection do I need to measure?
• How many samples per day will I measure?
• Can I pull a vacuum with my sample?
• What elements do I need to measure?
• What type of flexibility do I need for multiple sample types?
• What size features or samples do I need to measure?
• How much money do I have?

As you can see there are many questions to answer and many options for XRF instruments. The more you know about what you want to measure, the better you can narrow down your search for the proper instrument.

XRF is a very powerful technique but you do need to get the proper tool for the job.
Happy hunting and good luck!

Seeing is Believing?

Dr. René de Kloe, Applications Specialist, EDAX

A few weeks ago, I participated in a joint SEM – in-situ analysis workshop in Fuveau, France with Tescan electron microscopes and Newtec (supplier of the heating-tensile stage). One of the activities during this workshop was to perform a live in-situ tensile experiment with simultaneous EBSD data collection to illustrate the capabilities of all the systems involved. In-situ measurements are a great way to track material changes during the course of an experiment, but of course in order to be able to show what happens during such an example deformation experiment you need a suitable sample. For the workshop we decided to use a “simple” 304L austenitic stainless-steel material (figure 1) that would nicely show the effects of the stretching.

Figure 1. Laser cut 304L stainless steel tensile test specimen provided by Newtec.

I received several samples a few weeks before the meeting in order to verify the surface quality for the EBSD measurements. And that is where the trouble started …

I was hoping to get a recrystallized microstructure with large grains and clear twin lamellae such that any deformation structures that would develop would be clearly visible. What I got was a sample that appeared heavily deformed even after careful polishing (figure 2).

Figure 2. BSE image after initial mechanical polishing.

This was worrying as the existing deformation structures could obscure the results from the in-situ stretching. Also, I was not entirely sure that this structure was really showing the true microstructure of the austenitic sample as it showed a clear vertical alignment that extended over grain boundaries.
And this is where I contacted long-time EDAX EBSD user Katja Angenendt at the MPIE in Düsseldorf for advice. Katja works in the Department of Microstructure Physics and Alloy Design and has extensive experience in preparing many different metals and alloys for EBSD analysis. From the images that I sent, Katja agreed that the visible structure was most likely introduced by the grinding and polishing that I did and she made some suggestions to remove this damaged layer. Armed with that knowledge and new hope I started fresh and polished the samples once more. And I had some success! Now there were grains visible without internal deformation and some nice clean twin lamellae (figure 3). But not everywhere. I still had lots of areas with a deformed structure and whatever I tried I could not get rid of those.

Figure 3. BSE image after optimized mechanical polishing.

Back to Katja. When I discussed my remaining polishing problems she helpfully proposed to give it a try herself using a combination of mechanical polishing and chemical etching. But even after several polishing attempts starting from scratch and deliberately introducing scratches to verify that enough material was removed we could not completely get rid of the deformed areas. Now we slowly started to accept that this deformation was perhaps a true part of the microstructure. But how could that be if this is supposed to be a recrystallised austenitic 304L stainless steel?

Table 1. 304/304L stainless steel composition.

Let’s take a look at the composition. In table 1 a typical composition of 304 stainless steel is given. The spectrum below (figure 4) shows the composition of my samples.

Figure 4. EDS spectrum with quantification results collected with an Octane Elite Plus detector.

All elements are in the expected range except for Ni which is a bit low and that could bring the composition right at the edge of the austenite stability field. So perhaps the deformed areas are not austenite, but ferrite or martensite? This is quickly verified with an EBSD map and indeed the phase map below confirms the presence of a bcc phase (figure 5).

Figure 5. EBSD map results of the sample before the tensile test, IQ, IPF, and phase maps.

Having this composition right at the edge of the austenite stability field actually added some interesting additional information to the tensile tests during the workshop. Because if the internal deformation in the austenite grains got high enough, we might just trigger a phase transformation to ferrite (or martensite) with ongoing deformation.

Figure 6. Phase maps (upper row) and Grain Reference Orientation Deviation (GROD) maps (lower row) for a sequence of maps collected during the tensile test.

And that is exactly what we have observed (figure 6). At the start of the experiments the ferrite fraction in the analysis field is 7.8% and with increasing deformation the ferrite fraction goes up to 11.9% at 14% strain.

So, after a tough start the 304L stainless steel samples made the measurements collected during the workshop even more interesting by adding a phase transformation to the deformation. If you are regularly working with these alloys this is probably not unexpected behavior. But if you are working with many different materials you have to be aware that different types of specimen treatment, either during preparation or during experimentation, may have a large influence on your characterization results. Always be careful that you do not only see what you believe, but ensure that you can believe what you see.

Finally I want to thank the people of Tescan and Newtec for their assistance in the data collection during the workshop in Fuveau and especially a big thank you to Katja Angenendt at the Max Planck Institute for Iron Research in Düsseldorf for helpful discussions and help in preparing the sample.

EBSD in China

Sophie Yan, Applications Engineer, EDAX

EBSD in China is a big topic and it may sound as though I am not qualified to judge or to summarize the current situation. However, as I have worked with EBSD applications for several years, I have personal experience to share. More than ten years ago, I didn’t know about EBSD when I was studying the microstructure of materials. I was in Shanghai at that time and the environment was kind of open. It is probably that at that time in China: very few people knew about EBSD. Today the situation has changed enormously after just after 10+ years. Most researchers now try to put EBSD on their microscope. Microscopes including EDS and EBSD capability are standard in Chinese universities.

As an Applications Engineer, I visit research organizations, companies, and factories. I meet customers from many different backgrounds. Some of them are experts but more are new to microanalysis, especially students from science and engineering universities. They may each have a different focus, but they all have high expectations of EBSD. The professors care about the functions which can solve their issues. If there is currently no such function, then they often ask if we can add it. Entry level users prefer to learn how to operate the microscope and detectors quickly so that they get their results as soon as possible. The most frequent question asked is, what can EBSD do? Then I begin my introduction and I see that they become more and more interested. Sometimes they have high expectations. For example, when I demonstrate stress/strain analysis, I am often asked how to get stress value. This is a common misunderstanding because as an indirect way technique, EBSD can show the strain trend of materials, but it is beyond it to measure stress value.

My routine work includes introduction and training. Over a period of time, I can see a newcomer becoming more experienced and getting his own results, which makes me proud as a supporter. Whereas I care about the EBSD technology itself, the customers are more interested in learning how to use it in their work to solve some of their analysis challenges. They often give me new ideas and make me aware of other areas besides pure technology, for example, how to remove the users’ initial fear for EBSD. As a student majoring in material science I thought crystallography was very different from the reality I now understand. As a ‘teacher’ I am not focused on how to keep our users’ interest on EBSD and reminding to them to use it regularly. Fortunately, social media has improved the speed and consistency of our communication. When issues are solved quickly, people think the EBSD technique is less difficult. Effective communication contributes to the technology transfer.

The level of adoption of EBSD hardware in China is excellent, but the usage of and research into the technique is still in its infancy. I have spoken to many people about this issue. The interesting thing is that outsiders tend to give an optimistic perspective. An Australia professor told me several years ago that we should be taking a longer-term view and that there would probably be, a tremendous change in the next ten years. Quantitative results make a qualitative change. I hope he is right!

Fortunately, EBSD usage in China has increased greatly and continues to increase, which shows us a promising future.

 

 

 

Water, Sand and Salt, and Why We Care About Compounds

Tara Nylese, Global Applications Manager, EDAX

Somewhere around the age of five years old, many of us learn that another way to identify water is by the molecular name, H2O. This usually leads to more questions like: ‘What is H?’, ‘What is O?’, ‘How does that make water?’, ‘Why should I care?’. Over the years, we grow into more advanced chemistry students exploring topics like compound formulas, and we learn that the world we live in is made up of complex associations of combined atoms. A chemical compound is a substance that is composed of two or more chemical elements. The reason that we should care about compounds is that an element such as Oxygen (O) can be very different if it is associated with Hydrogen into H2O to make water, or as SiO2, which is Silicon Dioxide that makes up sand on a beach, or as Fe2O3, which is ferric oxide, loosely known as rust on steel. Therefore, as microanalysts, we should pay close attention to compounds because the elements alone do not always tell us the complete nature of the material we’re analyzing.

Once we grow into an “expert scientist,”* we become deeply entrenched in the details of microanalysis, and we often forget to take a step back to see the big picture. For example, as an EDS analyst, I look at the spectrum below and I think “what a nice sodium peak” or “hmm, am I picking up Al due to scatter at variable pressure?” But unless I’m using it for an introduction to a microscopy and microanalysis student lecture I don’t often simply call it what it is, and that is NaCl, or salt.

Next, we look at the electron image at very low mag and that gives us a better contextual understanding that it is a grain of salt.

When we look back at the spectrum again with a big picture view, we recognize that the main elements present in the spectrum are Na and Cl, and that they make up the compound NaCl, or salt.

In follow up to my recent webinar, I received a lot of questions asking “What are CompoMaps?” and “How can I use CompoMaps?” I was glad to see so much interest in such a valuable routine, and I do hope that users of every level can use this “Compound” view to understand their materials more deeply. To answer the first question, “CompoMaps” is a sophisticated software routine that creates a display of the elemental composition of each pixel. That is, the intensity of the pixel display color is a direct representation of the peak intensity of an element. It is helpful when there is a trace amount of an element, because the routine separates the peak from the background, removing the noise and intensifying the signal. It is perhaps most useful for separating element peaks where there is ambiguity whether there is one element, or another. In the example shown below, I was collecting this data when I happened to get a chance to web connect with an earth sciences professor. After he saw the before and after, he commented that the “after” made much more sense because those two elements would not likely be in combination together in any mineral.

The results here show that Phosphorus in green and Zirconium in purple are definitely located in two different phases.

Before CompoMaps:
After CompoMaps:
Superimposed into one image:
What we didn’t see in the webinar was the Oxygen map, shown here for the first time:
The display shows both with (right) and without (left) the Phosphorus and Zirconium superimposed, and this gives us a better understanding about the compound, since Oxygen is present with these elements. After full investigation of all element maps, we find that the two phases are Ca5(PO4)3F, or fluorapatite and ZrSiO4, or Zircon.

Finally, the answer to the question, “How can I use CompoMaps?”, is easy. This is a routine that EDAX has had in all of our software packages from Genesis to TEAM™ (as Net Maps) and now in APEX™. The routine has been optimized for APEX™ with 64-bit architecture and advanced processing capability, along with an easy to use workflow for results in live-time. So, give it a try and see what you can find!

*My personal opinion is that we should never let ourselves call ourselves experts, lest we forget that there is always something new to learn.

Looking At A Grain!

Sia Afshari, Global Marketing Manager, EDAX

November seems to be the month when the industry tries to squeeze in as many events as possible before the winter arrives. I have had the opportunity to attend a few events and missed others, however, I want to share with you how much I enjoyed ICOTOM18*!

ICOTOM (International Conference on Texture of Materials) is an international conference held every three years and this year it took place in St. George, Utah, the gateway to Zion National Park.

This was the first time I have ever attended ICOTOM which is, for the most part, a highly technical conference, which deals with the material properties that can be detected and analyzed by Electron Backscatter Diffraction (EBSD) and other diffraction techniques. What stood out to me this year were the depth and degree of technical presentations made at this conference, especially from industry contributors. The presentations were up to date, data driven, and as scientifically sound as any I have ever seen in the past 25 years of attending more than my share of technical conferences.


The industrial adaptation of technology is not new since X-ray diffraction has been utilized for over half a century to evaluate texture properties of crystalline materials. At ICOTOM I was most impressed by the current ‘out of the laboratory’ role of microanalysis, and especially EBSD, for the evaluation of anisotropic materials for quality enhancement.

The embracing of the microanalysis as a tool for product enhancement means that we equipment producers need to develop new and improved systems and software for EBSD applications that will address these industrial requirements. It is essential that all technology providers recognize the evolving market requirements as they develop, so that they can stay relevant and supply current needs. If they can’t do this, then manufacturing entities will find their own solutions!

*In the interests of full disclosure, I should say that EDAX was a sponsor of ICOTOM18 and that my colleagues were part of the organizing committee.

Looking at the World of Microanalysis in Color

Tara Nylese, Global Applications Manager, EDAX

Several years ago, I was talking to a customer, who asked whether we could change the color scheme of the EDAX TEAM™ software. He said was that it was hard for him to tell the difference between the spectrum background and the cursor. I replied, “Well, the cursor is a lime green and the background is more like a gray-gre…..Oh, wait, you’re colorblind, aren’t you?” Surely enough he was, and while I can’t “see” his perspective, I can listen to and respect it. Thus, the motivation of this blog is to let our customers know that we in Applications listen to them and take their needs seriously.

In this specific case, I am happy to report that we just recently received feedback on the new EDAX APEX™ software, and one comment was that the user really liked the “contrast” of the red spectrum on the white background – see the image below.

More generally, it is one main goal of the EDAX Applications team to make sure that we capture the “real world” customer feedback and incorporate it as much as possible into future product enhancements, bug fixes and new generations of products. Each of our Worldwide Apps team members can talk to upwards of ten customers a week. These conversations are usually in interactions such as support calls, training sessions and demos. At each opportunity, we hear tremendously valuable real-world customer perspective, and very often we learn what we can’t “see” ourselves. Often, if I’m asked to share my thoughts, my words are just a colorful patchwork of years of customer ideas all melded into a microscopy amalgam.

Customer perspective is so important, in fact, that it is a cornerstone of the EDAX App Lab Mission Statement. A few years ago, I compiled about three pages of descriptions of what people thought of when they thought of Apps, and then condensed them down into the following statement that hangs on our HQ App Lab walls.

The EDAX US App Lab uses technical expertise and creativity plus a strong focus on understanding the needs of our internal and external customers to drive excellence in innovative analytical solutions. The applications group supports company-wide efforts to provide real-life value and benefits to our customers which differentiate our products in materials analysis.

Now to get back to the colors which are available for maps in our software. One of the lesser known functions is the ability to select and edit your color palette:

Using this option, you can choose from a 40-color palette, seen here. Remember to click on the element in the periodic chart first, then select your color.

Since I brought up the topic of colorblindness, I’ll also use a colorblind app that simulates how a Red/Green colorblind person sees the world (or our color palette).

Note the green color of O and P, and see how closely it compares to the yellow color of the lanthanide/actinide series!

Finally, to summarize the Applications message: to our current customers – thank you for sharing your thoughts; to all our applications team colleagues – thank you for gathering so much wide-ranging information and promoting the importance of it internally, and to all our future customers – when you chose EDAX, you’re choosing to join a dynamic microanalysis company, which strives to develop the most meaningful features and functions to meet your microanalysis needs.

How to Increase Your Materials Characterization Knowledge with EDAX

Sue Arnell, Marketing Communications Manager, EDAX

The EDAX Applications and Product Management teams have been very busy offering free ‘continuing education’ workshops in September and October – with a great global response from our partners and customers.

At the end of September, Applications Specialist Shawn Wallace and Electron Backscatter Diffraction (EBSD) Product Manager Matt Nowell joined 6 additional speakers at a ‘Short Lecture Workshop for EBSD’, sponsored by EDAX at the Center for Electron Microscopy and Analysis (CEMAS) at The Ohio State University. The participants attended sessions ranging from ‘EBSD Introduction and Optimization of Collection Parameters for Advanced Application’ to ‘The Dictionary Approach to EBSD: Advances in Highly-Deformed and Fine-Grained Materials’.

Feedback on this workshop included the following comments, “This was a great learning opportunity after working with my lab’s EDAX systems for a couple of months”; “I like the diversity in the public and the talks.  I was very pleased with the overall structure and outcome”; and “Great! Very helpful.”

Matt Nowell presents at the ‘Short Lecture Workshop for EBSD’ at CEMAS, OSU.

In mid-October, EBSD Applications Specialist, Dr. Rene de Kloe traveled to India for a series of workshops on EBSD at the Indian Institute of Science (Bangalore), the International Advanced Research Center (Hyderabad), and the Indian Institute of Technology (Mumbai). Topics discussed at the sessions included:

• Effects of measurement and processing parameters on EBSD
• The application of EBSD to routine material characterization
• Defining resolution in EBSD analysis
• Three Dimensional EBSD analysis – temporal and spatial
• Advanced data averaging tools for improved EDS and EBSD mapping – NPAR™
• Microstructural Imaging using an Electron Backscatter Diffraction Detector – PRIAS™
• Transmission EBSD from low to high resolution

Dr. René de Kloe presents at one of three recent workshops in India.

According to our National Sales Manager in India, Arjun Dalvi, “We conducted this seminar at different sites and I would like to share that the response from all our attendees was very good. They were all eager to get the training from Dr. René and to take part in very interactive Q and A sessions, in which many analysis issues were solved.”

Global Applications Manager Tara Nylese was at the Robert A. Pritzker Science Center in Chicago, IL last week to give a presentation on “Materials Characterization with Microscopy and Microanalysis” for the Illinois Institute of Technology. “In this lecture, we started with a basic introduction to electron microscopy, and then dived deeper into the fundamentals of X-ray microanalysis. We explored both the basics of X-ray excitation, and how to evaluate peaks in an X-ray spectrum. From there, we looked at applied examples such as composition variation in alloys, chemical mapping of components of pharmaceutical tablets, and some fascinating underlying elemental surprises in biological materials.”

Finally, today we have 50 participants at the Geological Museum in Cambridge, MA for a training workshop given by Dr. Jens Rafaelsen and sponsored by Harvard University on “Taking TEAM™ EDS Software to the Next Level” * Presentation topics include:

• Basic operation of the TEAM™ EDS Analysis package
• How to get the most out of TEAM™ EDS Analysis
• Advanced training
• Tips and Tricks using TEAM™ EDS Analysis

Dr. Jens Rafaelsen presents at the Harvard workshop.

Here at EDAX, we are keen to provide our customers, potential customers, and partners with opportunities to improve their knowledge and polish their skills using the techniques, which are central to the EDAX product portfolio.  Our EDS, EBSD, WDS and XRF experts enjoy helping with regular training sessions, webinars, and workshops. If you would like to be included, please check for upcoming webinarsworkshops, and training sessions at www.edax.com.

*A video of these workshop sessions will be available from EDAX in the coming weeks.