Powder micro-XRD of small particles

Joseph R. Swidera
McCrone Associates, Inc., Westmont, Illinois 60559

Received 20 October 2009; accepted 29 December 2009 The increasing use of microanalysis techniques to analyze particles has demanded more rapid phase identification methods for samples in the 10 m size range. The XRD analysis of such particles is routinely accomplished using a Rigaku combination instrument combined with particle handling methods. Several case studies show the variety of material analysis problems that can be solved with this technique including identification of multiple mineral phases, corrosion components, and paint samples. © 2010 International Centre for Diffraction Data. DOI: 10.1154/1.3308434 Key words: micro-XRD, particle phase analysis, microanalysis


Uses of X-ray diffraction XRD range from the fundamental determination of single-crystal structure to the practical differentiation of elementally identical compounds. The conditions for these two uses overlap when the phase identification of small particles with the sizes of single crystals is desired, which is powder diffraction of small particles. The use of micro-XRD in a laboratory can be limited to particle size because of instrument design, sample mounting, and X-ray output. This has increased the implementation of intense X-ray sources in powder XRD instruments—typical sealed tubes are being replaced in more laboratories with rotating anode sources. This is complemented by the increased number of XRD instruments at synchrotron sources around the world see, for instance, Fujiwara et al. 2000 , Salbu et al. 2001 , and Castelnau et al. 2000 . In light of all these advancements, the demand for routine use of an in-house instrument to analyze small particles not for singlecrystal information but for powder analyses has increased Salbu et al., 2002; Nel et al., 2006 . At McCrone Associates, Inc., the microanalysis of small particles in the 10 m size range is commonplace. Typical microanalysis techniques are employed on a daily basis such as scanning electron microscopy SEM equipped with elemental analysis via energy-dispersive X-ray spectrometry EDS , micro-Fourier transform infrared spectroscopy, and micro-Raman spectroscopy in addition to polarized light microscopy. A need arose to further characterize these particles by micro-XRD. The micropowder XRD analysis would require a powerful X-ray source preferably with beam focusing to compensate for the small sample size as well as a stable mounting scheme. In our laboratory we have successfully coupled a rotating anode XRD instrument with decades of particle analysis experience to create a powder micro-XRD instrument able to analyze particles in the 10 m size range.

must have a sufficiently high X-ray power, a beam size on the order of the sample size, and a mounting scheme that is reproducible and allows for easy sample exchange. A detailed description of the instrument and sample preparation has been given elsewhere Swider, 2009 and is briefly described here. The instrument implements a unique configuration of a Rigaku MicroMaxx-007 Cu rotating anode source with focusing optics, an imaging plate for “filmless” X-ray detection, and a 1/4-chi goniometer. The copper rotating anode operates at its maximum of 40 kV/20 mA which delivers an intensive beam to an optical system for focusing. The beam is further collimated with a 0.1 mm aperture. Detection is accomplished with a Rigaku R-AXIS SPIDER area detector. The detector system uses a curved imaging plate that is read by a laser scanning readout system in about 1 min. The sample is mounted in a 1/4-chi goniometer with movements capable in , , and positions. Rigaku software is used to record the diffraction image from the laser readout and the operator can determine the area to integrate for a 2 versus intensity plot. This plot is read into MDI JADE 9.0 software for data interpretation. Samples in the 10 m size range require skill to mount and need to be on a sample holder that will not interfere with sample diffraction. Our cleanroom microscopists routinely manipulate particles for a variety of microanalyses and mount XRD particles before or after these techniques. The particles are mounted on in-house fabricated glass fibers, about 5 to 20 m in diameter, with a small amount of soluble gum. The fiber and particle, secured in a brass pin for mounting on the goniometer head, are viewed using a CCD camera and video screen. Crosshairs are set at the focus position on the screen and the particle is aligned to coincide with them.

III. CASE STUDIES A. Mineral samples


The analysis of small particles for powder diffraction without a synchrotron source requires significant changes over a typical powder instrument. A powder microinstrument

Electronic mail: jswider@mccrone.com Powder Diffraction 25 1 , March 2010

Small particles of unknown mineral samples were first analyzed by EDS for elemental compositions. The particles were then mounted on fibers for micro-XRD. The particles ranged from 20 down to 7 m in size were analyzed in 30 to 90 min exposures. A summary of the samples is provided in Table I. In addition to confirming the single-phase identification of several samples, three samples contained multiple phases: a 20 m particle with rutile, quartz, and ilmenite
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Lead paint detection We received two samples of spall from indoor frescoes. 25. Sample size m 20 14 10 8 7 Phases detected Rutile. A small amount of corrosion was seen on the surface of one particular contact and the client requested that we identify the corrosion. An approximately 20 m size particle of corrosion was removed and mounted on a thin glass fiber for microXRD. and quartz but no gypsum. Although the detection of lead in paint is relatively simple with EDS and with handheld X-ray fluorescence devices. a 14 m particle with zircon and thorite. m particle with corun- Accelerated testing by exposing a material extreme light. No. environmental were the cause of the spall Figure 4 .TABLE I. humidity. A number of legal cases Figure 1.. and ilmenite identified. and chemicals is commonly used in manufacturing to test the longevity of products. B. The result Figure 3 was a nickel sulfate hydrate. The information showed that the two murals were composed of approximately the same material and perhaps nonmaterial reasons i. Color online Micro-XRD pattern of 10 dum and baddeleyite identified. D. Color online Micro-XRD pattern of 20 quartz. m particle of corro- Powder Diffr. The tests can produce failed parts and insight into which components are the weakest. The detection of lead pigment in house paint has been the subject of numerous lawsuits since its ban in the 1970s. 1. The particles were first analyzed for elemental compositions by EDS and similar elements were found in both samples. portlandite. March 2010 69 . Particles that were white or off-white were selected for micro-XRD. Corrosion of accelerated testing circuits Figure 2. aragonite. the characterization of the lead component as white lead carbonate hydrocerussite Pb3 CO3 2 OH 2 and cerussite PbCO3 still requires phase identification. 90 min exposure. The other sample sample 2 was from a fresco in the same building but with no signs of spall. quartz. One sample sample 1 was removed from a fresco that had significant spall and the sample contained some of the spall itself. We received a circuit board from an unnamed device that was exposed to such a test and then would not function. Fresco particles The samples were examined using a stereomicroscope and found to be agglomerates of white and semiopaque particles. The two samples showed similar phases including calcite. Figure 3. The client asked us to determine if there was any difference between the two samples and in particular if the spall sample had gypsum present. 69 m particle with rutile.e. and ilmenite Zircon and thorite Corundum and baddeleyite Perovskite Zirkelite present Figure 1 . a combination of the nickel electrode and the sulfur dioxide present during the accelerated testing. 30 min exposure. 15 min exposure. and a 10 m particle with the phases of corundum and baddeleyite confirmed Figure 2 .. Vol. Color online Micro-XRD pattern of 20 sion. List of mineral samples. C.

It was noticed in layer 4 of sample 3 that small particles were rich in a variety of elements. Swider 70 . Figure 4. and if lead is present they are mounted for micro-XRD.TABLE II. The decision to remove a sample of blue-black material from sample 3 arose from the SEM/EDS examination. window sill and door jamb . where 20 or more layers of paint are present Figure 5 . Color online Light microscope image of a polished cross section of a typical architectural paint sample. and cinnabar Cobalt tin oxide sample preparation technique involves removing particles from specific layers giving specificity to their history in the structure. the samples arrive as polished cross sections. 2 the Particle analysis techniques are very applicable to the art conservation and conservation science fields. The removed particles are checked for the presence of lead by EDS. 1. Color online Micro-XRD patterns of 15 to 25 m particles from two fresco samples. or entire architectural structures i. A single particle from this layer was removed and showed cobalt-tin ox- Figure 5. March 2010 Figure 6. hydrocerussite. We have routinely identified a number of samples with the white lead carbonate pigment using micro-XRD. most notably tin and cobalt Figure 6 .e. The samples were all close to 40 m in size and produced clear patterns in 15 min exposures or less. No. the large amount of copper that would be associated with another azurite layer was not seen. 70 Powder Diffr. More commonly. E. the method has other advantages: 1 micro-XRD is nondestructive and the particles can be further analyzed by other parties for confirmation. Table II provides the information about the micro-XRD samples. cross sections. The layers with significant lead content are identified and particles removed from each for micro-XRD—some layers only a few micrometers thick. Vol. Micro-XRD samples from a 15th century Spanish panel painting. The major concern in analyzing materials from cultural artifacts is to leave the artifact virtually unchanged. Size m 45 40 45 Sample 1 2 3 Layer 2 2 4 Color Blue Pink Blue-black Major phases Azurite Cerussite.. but this can limit the analyses that can be performed.. 25. showing their similarity in identified components and the absence of gypsum. and 3 the particles removed can be as small as 10 m. The samples of chips are examined using a stereomicroscope and white particles selected as candidates. Joseph R. Samples from houses in question of containing white lead carbonate can be in paint chips. leaving the original cross section virtually intact. In addition to the indisputable evidence that white lead carbonate is present. Each of these cross sections was analyzed by SEM/ EDS and particles were removed from specific layers for micro-XRD a paper discussing the full extent of the analyses will be given in a future publication . The azurite for blue and the combination of cinnabar the pigment vermilion and hydrocerussite white lead carbonate for flesh tones were typical and in ample amount through each sample’s cross section. In addition. Sampling artifacts for material analysis should involve removing the smallest amount of material possible. 15th century Spanish panel painting stipulate that detection of lead is not sufficient-certain layers in paint cross sections need to be positively identified as white lead carbonate. Color online Backscattered electron image of sample 3 with the particle removed from layer 4 indicated. A conservator researching and conserving a 15th century Spanish panel painting had questions about pigments found in certain cross sections from the painting. these cross sections were notably loose and in areas were restoration was needed.

http://www.Figure 7. Y. Color online Micro-XRD pattern of a particle from sample 3.. The combination of expert particle handling and mounting by a skilled cleanroom staff and a state-of-the-art combination rotating anode XRD system has proven invaluable in obtaining fullparticle characterization on a daily basis. Appl. Janssens. layer 4 of the 15th century panel paining.. I. S. T.. Simionovici. 2000 . 25. “Synchrotron radiation X-ray powder diffractometer with a cylindrical imaging plate. Snigirev. Samples from a variety of projects have greatly benefited in quickly identifying phases in small particles. T. Watanuki. The routine rapid analysis of particles in the 10 m size range continues to be accomplished in our laboratory. Ishii.” Modern Microscopy. donated by the author is shown in Figure 8. K... Drakopoulos. T. Instrum. and Katayama. Instrum..... Lind. Nel.. B.. and Bacroix. and Hay.. Y.. Daicho..” J. A 467–468. Mori. Methods Phys. B.. 1. Kikegawa. Janssens. T.. Snigireva. ide Figure 7 the material used for Cerulean Blue. in fact it confirmed the conservator’s suspicions that areas of the painting were the result of later restorations. F. O. 119. A. and Snigirev A. Nakao. 147–152.” Proceedings of Actinide XAS Workshop unpublished . Ohwada. Vol. Fujiwara.. Ungar. 2002 . T.. 1241– 1245. Chauveau. 2009 . 489–495. Figure 9. O. Kitamura.. H. S. Swider. These results did not prove the painting was not 15th century. T. M..asp?article 94 . 2006 . 2001 . 2000 . “High energy X-ray microscopy for characterisation of fuel particles. Drakopoulos. Lau. Salbu. “SR-based X-ray microbeam techniques utilized for solid-state speciation of U in fuel particles. Weitkamp. p. Suematsu. M. Oughton. C.” Key Eng.. A. Color online Light microscope image of stained tooth sample. Adams. CONCLUSION The focused beam combined with its intensity makes it a good XRD tool for small areas on samples. A. O. 1249–1252. I. A. F. C.. J. “Non-destructive micro-X-ray diffraction analysis of painted artefacts: Determination of detection limits for the chromium oxide-zinc oxide matrix... Res.. K.modernmicroscopy. 33. Drakopoulos. “Micro powder X-ray diffraction in the laboratory. V. D. Mater. C. B 251. Kawada... Hanabusa. Color online Micro-XRD patterns of stained top and unstained bottom areas of tooth. D. Lind. H.. Krekling. March 2010 71 . Murakami. The sample was positioned in the beam in two positions: one with only white in the focus and the other in the dark area with 2 min exposures each. I... A. Fujii. a pigment not marketed for artists until about the 1860s. T. Surface samples IV. H. B. 71 Powder Diffr. K.... Snigireva.. Simionovici. A section of decayed tooth 4 mm. Methods Phys. Snigirev.. and Kashparov.” Nucl. Snigireva. Krekling. H. Res. No.” Nucl. A.. P. H. T. Castelnau. “Single grain analysis of strain hardening and internal stresses in cold rolled IF-Ti steel with a new high-resolution microdiffraction technique. Schorer. K. the pattern clearly shows the presence of cobalt-tin oxide. The composite patterns shown in Figure 9 reveal the clear difference—and an evidence of tooth decay by the presence of calcium oxalate—between the tooth and its surface coating.. Shimomura. 177–180.. Figure 8. T. Salbu. C. R. D.com/main.. Matsubara.. Crystallogr.. M. O....