A novel type of X-ray collimation system attached to commercial powder diffractometers makes the structural characterization of nanomaterials possible in a wide size range from <0.1 to 100 nm by combination of the small- and wide-angle X-ray scattering techniques. There is no dead interval in the detection between the small- and wide-angle regimes. This device can be attached to any existing 'θ/θ' powder diffractometer, providing a multi-functional small- and wide-angle X-ray scattering/diffraction (SWAXS) apparatus. After proper alignment and adjustment, the device can be removed and re-attached at any time to switch between normal and SWAXS functions. Copyright © International Union of Crystallography 2013

Attila Bóta

Binnemans

Broennimann

Haubold

Kratky

Laggner

Schmitt

Singh

English

Bóta, Attila

Repository of the Academy's Library

electronic reprintJournal ofAppliedCrystallographyISSN 0021-8898Editor: Anke R. Kaysser-PyzallaDevelopment of powder diffraction apparatus for small-angleX-ray scattering measurementsAttila Bo´taJ. Appl. Cryst. (2013). 46, 573–576Copyright c© International Union of CrystallographyAuthor(s) of this paper may load this reprint on their own web site or institutional repository provided thatthis cover page is retained. Republication of this article or its storage in electronic databases other than asspecified above is not permitted without prior permission in writing from the IUCr.For further information see http://journals.iucr.org/services/authorrights.htmlJournal of Applied Crystallography covers a wide range of crystallographic topics fromthe viewpoints of both techniques and theory. The journal presents papers on the applica-tion of crystallographic techniques and on the related apparatus and computer software.For many years, the Journal of Applied Crystallography has been the main vehicle forthe publication of small-angle scattering papers and powder diffraction techniques. Thejournal is the primary place where crystallographic computer program information ispublished.Crystallography Journals Online is available from journals.iucr.orgJ. Appl. Cryst. (2013). 46, 573–576 Attila Bo´ta · Powder diffraction apparatus for SAXS measurementslaboratory notesJ. Appl. Cryst. (2013). 46, 573–576 doi:10.1107/S002188981205162X 573Journal ofAppliedCrystallographyISSN 0021-8898Received 28 August 2012Accepted 21 December 2012# 2013 International Union of CrystallographyPrinted in Singapore – all rights reservedDevelopment of powder diffraction apparatus forsmall-angle X-ray scattering measurementsAttila Bo´taResearch Centre of Natural Sciences, Hungarian Academy of Sciences (RCNS-HAS), Institute of MolecularPharmacology, Department of Biological Nanochemistry, 1025 Budapest, Pusztaszeri u´t 59–67, Hungary.Correspondence e-mail: bota.attila@ttk.mta.huA novel type of X-ray collimation system attached to commercial powderdiffractometers makes the structural characterization of nanomaterials possiblein a wide size range from <0.1 to 100 nm by combination of the small- and wide-angle X-ray scattering techniques. There is no dead interval in the detectionbetween the small- and wide-angle regimes. This device can be attached to anyexisting ‘/’ powder diffractometer, providing a multi-functional small- andwide-angle X-ray scattering/diffraction (SWAXS) apparatus. After properalignment and adjustment, the device can be removed and re-attached at anytime to switch between normal and SWAXS functions.1. IntroductionLarge facilities such as synchrotrons and neutron sources make thestructural characterization of nanomaterials possible worldwide bythe use of small-angle scattering (SAS) techniques. The successfulrealization of measurements at these research centres, however,requires preliminary SAS experiments. Unfortunately, small-angleX-ray scattering (SAXS) laboratory apparatuses are not so widelyused as X-ray powder diffraction (wide-angle diffraction X-rayscattering, XRD) equipment; therefore SAXS experiments arefrequently hampered.In laboratory practice, the so-called ‘compact Kratky’ camera isgenerally used (Kratky & Glatter, 1982; Kratky & Stabinger, 1984;Laggner & Mio, 1992). Despite its many advantages, the applicationof the unmodiﬁed version of this construction has some restrictions(extended reﬂection geometry is not possible; no wide-angle scat-tering range is available, or if it is, there is a dead interval between thesmall- and wide-angle regimes; measurements can be made undervacuum only). Recently, a modiﬁed Kratky camera has allowed amore extended scattering range, up to 40 (SAXSess mc2; AntonPaar, 2012). Besides the Kratky camera, however, new point-focusSAXS cameras are presenting novel possibilities for nanoresearch(http://www.bruker-axs.com/nanostar.html; http://www.rigaku.com).In SAXS measurements the adjustment of the ﬁne proﬁle of theX-ray beam is the most crucial point; therefore the stable and robustcollimation block of the Kratky camera has now been applied in anew type of SAXS camera (Mallett et al., 2012).Here we report a device with which an existing XRD apparatus canprovide important nanostructural information by using a minor, butpowerful, technical development. The upgrading of the XRD appa-ratus described below provides a multi-functional powder diffractioninstrument (Bo´ta et al., 2005). This construction allows a continuousscan in an extremely wide range from small to wide angles (2min <0.1, 2max ’ 130) without any dead interval in the detection. Thisrange corresponds to a real-space resolution from about 0.1 to 100(200) nm, which is typical in materials sciences. For SAXS measure-ments this device was implemented on operating apparatuses withoutany change or reduction in their original functions.2. Experimental setupFor SAXS measurements our device was implemented on two typesof commercially available XRD apparatuses: an XRD 3003 TT (/)diffractometer from GE Germany (Ahrensburg; previously Seifert)and an X’Pert powder diffractometer from PANalytical (GEMeasurement & Control, 2012; http://www.pananalytical.com). Forthe detection of SAXS, two main parts were constructed: a collima-tion system and a vacuum tube. The latter was mounted onto thedetector directly. The collimation system contains three parts: twoentrance slits (0.2 and 0.3 mm, for initial limitation of X-rays), aSoller collimation system (to achieve a parallel beam) and a specialSAXS collimation block. The latter is fundamental in adjusting theincident beam in both the horizontal and the vertical directions, and isshown schematically in Fig. 1. The SAXS collimation block is made ofalumina to achieve minimal weight and is placed inside a frame. It hasfour edges (made of iron–tungsten steel) for vertical collimation andthree slits with ﬁxed openings for horizontal limitation. The positionof the frame can be adjusted in order to achieve the correct alignmentwith respect to the centre of gravity of the incoming X-ray beam.Additional ﬁne adjustment of the block inside the frame makes therequired cut of the beam possible. The idea of constructing thecollimation block in this way was inspired by combining the operatingprinciples of the Kratky collimation system with the slits used atsynchrotron beamlines.The experimental setup of the small- and wide-angle measure-ments for the XRD 3003 TT diffractometer in the transmissionarrangement is also presented in Fig. 1. The installation wascompleted with a vacuum tube to ensure a signiﬁcant reduction of thesmall-angle X-ray scattering in air. The collimation system wasmounted in the X-ray tube by taking the geometry and mechanicalspeciﬁcations of the goniometer into account.3. Experimental details and data processingThe Seifert and PANalytical apparatuses contain a 1.6 kW (operatedat 40 kV and 30 mA) and a 2.2 kW (operated at 40 kV and 30 mA)X-ray tube, respectively. Both are equipped with proportional gaselectronic reprintdetectors with exchangeable entrance slits, a ﬁne one for detectingthe beam proﬁle (0.001) and a broader one for measuring thescattering curves (0.01). Ni-ﬁltered Cu K radiation ( = 1.542 A˚)was used in both instruments. As the measurements were performedby using a slit collimation, the SAXS intensity curves were correctedfor line focus smearing considering the geometry of the beam proﬁle,using the direct method described by Singh et al. (1993).Point-focus small- and wide-angle X-ray scattering measurementswere made for reference on silver behenate at the synchrotronbeamline B1 of the storage ring DORIS III at HASYLAB/DESY,Hamburg, Germany (Haubold et al., 1989). The beam used was pointcollimated (1  0.7 mm) and monochromated to 9626.7 eV with anSi(311) double-crystal monochromator. The scattering pattern wasobtained by using two experimental setups with 883 and 3583 mmsample-to-detector distances. In the small- and wide-angle X-rayscattering regimes a two-dimensional (PILATUS 300k, Dectris Ltd,Switzerland) and a one-dimensional (MYTHEN, Dectris Ltd, Swit-zerland) detector were used, respectively (Broennimann et al., 2006;http://www.dectris.com; Schmitt et al., 2003). Radial scattering curveswere calculated from the images and normalized to absolute units.4. Experimental setup and performance4.1. Beam profile and background curveThis new type of collimation system provides a very narrow X-raybeam, which makes the measurement of small-angle scatteringpossible. The collimation is demonstrated in Fig. 2(a), presenting theX-ray beam proﬁle in the vertical direction. The measurement of theattenuated beam was carried out using copper ﬁlters. The ﬁneadjustment allows a sharp cut on the positive side of the proﬁle,whereby the ‘ﬁrst measurement point’ can be adjusted so that it fallsbelow 2 = 0.1, which extends the measurement in real space up to2 /qmin = 100 nm [q is the absolute value of the scattering vector,deﬁned as q = (4/) sin, where  = 0.1542 nm is the wavelength ofthe Cu K ﬂuorescence line]. For a better understanding, the proﬁleof the primary beam is also plotted in logarithmic scale (Fig. 2a, uppercurve). Without using any ﬁlter, we can observe the backgroundscattering in the extended 2 regime, shown in Fig. 2(b). For practicalreasons, the ﬁrst measurement point is at the lowest q value where thebackground intensity is 10–20 times higher than the nearly constantvalue observed at higher angles. The intensity is approximately 0.3counts per second (c.p.s.) between 2 and 14, and, as a consequence,the ﬁrst measurement point is 2 = 0.1 (1.75 mrad) (shown as insetsin Fig. 2).laboratory notes574 Attila Bo´ta  Powder diffraction apparatus for SAXS measurements J. Appl. Cryst. (2013). 46, 573–576Figure 2Vertical proﬁle of the collimated X-ray beam measured by using copper ﬁlters (a).Background scattering measured in small- and wide-scattering regimes (b).Figure 1Modiﬁed XRD 3003 T/T powder diffractometer (inset collimation block in frame)(a) and a schematic view of the novel SAXS collimation system (b). The position ofthe frame containing the block can be adjusted (blue arrows) with respect to theincoming beam. Further ﬁne adjustment can be made by a gentle tilting of the blockinside the frame (green arrow). All four edges (blue columns) can be positioned.electronic reprint4.2. SAXS of silver behenateFor a demonstration of SAXS measurements on the diffract-ometer, the scattering curves of silver behenate are presented inFig. 3. This material serves as a standard for q calibration at severalsynchrotron SAXS beamlines, because of its accurate periodicity of5.84 nm (Binnemans et al., 2004). The consequence of its one-dimensional arrangement is the appearance of small-angle X-raydiffraction (SAXD) peaks along the scattering proﬁle. Therefore, wecan detect the Bragg reﬂection in a number of orders on the scat-tering curves. Besides the SAXS curve detected in the XRD appa-ratus, a pattern obtained at a synchrotron station (DESY/HASYLAB/B1 beamline) is also plotted in Fig. 3. Comparing thesecurves, we can observe the smearing effect of the line focus of thecollimation, resulting in the broadening and deformation of the Braggreﬂections, especially in the case of the ﬁrst and the second orders.The desmeared SAXS curve is also plotted to compare the patternafter the reconstruction of results of a line focus beam proﬁle inrelation to the point-focused SAXS (B1) beamline. It is important tonote that the point-spread function of the PILATUS 300k detector islower than one pixel; thus no cross-talk exists between the neigh-bouring pixels, in contrast to the case of multiwire proportionalchamber gas detectors (Vaino et al., 2009, 2012).The advantage of this development is evident: an extended scancan be carried out covering both the small- and wide-angle regimes,referred to as small- and wide-angle X-ray scattering (SWAXS). Itmust be noted that SWAXS measurements are generally not feasibleat synchrotron SAXS stations. At the B1 beamline, it was possible toinsert the one-dimensional detector into the extremely large samplechamber, whereby the angular range of the measurement wasextended up to 2 = 40 (Vainio, 2012). One can see the higher ordersof small-angle diffraction of silver behenate even at 2 = 18, clearlydemonstrating the extended SAXS regime of scattering of thiscolloidal system. This feature cannot be observed by using aconventional compact camera with ﬁxed sample–detector distance(generally about 20 cm). In the wide-angle range (2 > 20), severalBragg reﬂections from the ‘a˚ngstro¨m’ length scale can be observed,clearly demonstrating that the hierarchical colloidal (‘nano’) andatomic structures overlap, and the extent of the SAXS/SAXD towardhigher scattering angles depends on the actual material studied. Wemention that for the q calibration in the wide-angle regime othermaterials, e.g. tripalmitin or silicium carbide, are also used but theseare not discussed here.On closer inspection, one can observe that the reﬂection peaks lieon a continuously decreasing baseline, which arises from the small-angle scattering of the heterodisperse ‘crystallites’ of silver behenate.To obtain information from a larger size range (>100 nm), theextension of SAXS measurement is required to an extremely small qregime, known as the ‘ultra-small-angle’ scattering regime (USAXS).A long collimation system (20 cm, which is twice as long as the oneshown in Fig. 1) was constructed for the XRD 3003 TT apparatus toallow for the measurement in this ‘ultra-small’ q regime. The SAXSmeasurement was executed in two different adjustments: with anextremely narrow proﬁle and with a slightly broader one, resulting intwo sections in the scattering curve. Their ﬁt to each other is alsodepicted in an inset in Fig. 3. One drawback of the extremely ﬁnebeam proﬁle is the reduced scattering intensity; therefore themeasurements in the ultra-small regime require substantially longerexposure times.Finally, we mention an additional opportunity of our developeddiffractometer, whereby the apparatus provides a unique extension instructural studies, namely, both transmission and reﬂectionmeasurements can be carried out. This combination is rarely acces-sible even at synchrotron stations because the beam and the detectorare positioned on one mutual axis. The precise collimation (ﬁrstmeasurement point at 2 = 0.1) makes the characterization ofmultilayered structures and interfaces possible by using reﬂectiongeometry.5. ConclusionBy the use of horizontal slits, the X-ray beam can be reduced to anearly point-focused one, providing further opportunities. Forexample, using a two-dimensional detector the measurement ofgrazing-incidence small-angle X-ray scattering is feasible. Once it isset up and aligned correctly, the device can be reversibly removedwith a simple movement (tilting the collimation system by the ﬁnemicrometer), which resets the original operating conditions of thediffractometer.The collimation block is a stable working tool; after its removal andreplacement, it provided practically the same quality measurements(tested in the case of the X’Pert apparatus). The parallel measure-ments executed on the upgraded diffractometers and the dedicatedsynchrotron SAXS beamline have served as a means of validation forour developed method.The author thanks Dr Alfried Haase and Mr Peter Stirnal (GEGermany, Ahrensburg) for making the development of the collima-tion system for the XRD 3003 TT apparatus possible, Mr FerencLaufer (Budapest University of Technology, Hungary) for his precisework to accomplish the developed device, Dr Ulla Vainio (DESY,HASYLAB, Helmholtz-Zentrum Geesthacht) for her valuablecooperation, especially for upgrading the B1 beamline for wide-anglediffraction, and Dr Tama´s Gro´sz (RCNS-HAS) for his help andcollaboration with the measurements carried out with the PANaly-tical X’Pert diffractometer. Finally, I thank gratefully Mr Andra´sWacha (RCNS-HAS) for his work in data processing. The validatingmeasurements on silver behenate were funded by the EuropeanCommunity’s Seventh Framework Programme (FP7/2007–2013)under grant agreement No. 226716 at DESY/HASYLAB. Thelaboratory notesJ. Appl. Cryst. (2013). 46, 573–576 Attila Bo´ta  Powder diffraction apparatus for SAXS measurements 575Figure 3Small- and wide-angle scattering/diffraction of silver behenate [measured on anXRD diffractometer (red) and at a synchrotron station (black)]. Inset (left): ultra-small-angle scattering; inset (right): desmeared and direct experimental (pointfocus/synchrotron) data. The intensity is given in absolute units (cm1) forsynchrotron data.electronic reprintinvestigation of model membrane systems was supported by theHungarian Scientiﬁc Research Fund and the National InnovationOfﬁce (Hungary) under grant agreement CNK-81056.ReferencesAnton Paar (2012). Modular Tool for Nanostructure Analysis: SAXSess mc2,http://www.anton-paar.com/Modular-Tool-for-Nanostructure-Analysis-SAXSess-mcsup2/SAXS/60_UK_en?product_id=320.Binnemans, K., Van Deun, R., Thijs, B., Vanwelkenhuysen, I. & Geuens, I.(2004). Chem. Mater. 16, 2021–2027.Bo´ta, A., Stirnal, P. & Haase, A. (2005). 19th ECIS Conference, 18–23September 2005, Geilo, Norway.Broennimann, Ch., Eikenberry, E. F., Henrich, B., Horisberger, R., Huelsen,G., Pohl, E., Schmitt, B., Schulze-Briese, C., Suzuki, M., Tomizaki, T.,Toyokawa, H. & Wagner, A. (2006). J. Synchrotron Rad. 13, 120–130.GE Measurement & Control (2012). Diffractometer System XRD 3003 TT,http://www.ge-mcs.com/download/x-ray/analytical-x-ray/GEIT-30154GB_diffractometer-system-xrd3003tt.pdf.Haubold, H.-G., Gruenhagen, K., Wagener, M., Jungbluth, H., Heer, H., Pfeil,A., Rongen, H., Brandenburg, G., Moeller, R., Matzerath, J., Hiller, P. &Halling, H. (1989). Rev. Sci. Instrum. 60, 1943–1946.Kratky, O. & Glatter, O. (1982). Editors. Small Angle X-ray Scattering.London: Academic Press.Kratky, O. & Stabinger, H. (1984). Colloid Polymer Sci. 262, 345–360.Laggner, P. & Mio, H. (1992). Nucl. Instrum. Methods Phys. Res. Sect. A, 323,86–90.Mallett, C., Le Magueres, P., Criswell, A. R., Ferrara, J., Suzuki, N., Degen, M.,Jiang, L. & Sasaki, K. (2012). BioSAXS-1000, Advanced Photon Source,Center for Nanoscale Materials, Electron Microscopy Center, UsersMeeting, Chicago, USA. Poster A-02.Schmitt, B., Bro¨nnimann, Ch., Eikenberry, E. F., Gozzo, F., Ho¨rmann, C.,Horisberger, R. & Patterson, B. (2003). Nucl. Instrum. Methods Phys. Res.Sect. A, 501, 267–272.Singh, M. A., Ghosh, S. S. & Shannon, R. F. (1993). J. Appl. Cryst. 26, 787–794.Vaino, U. (2012). Beamline: B1, HASYLAB, Hamburg, Germany, http://hasylab.desy.de/user_info/available_instruments/x_ray_scattering/b1.Vaino, U., Schubert, T., Botta, S., Blume, J., Wacha, A., Lohmann, M., Kracht,T. & Gehrke, R. (2009). New in situ SAXS/WAXS Setup and OtherRefurbishments at the ASAXS Beamline B1, HASYLAB. Annual Reports,HASYLAB, Hamburg, Germany.laboratory notes576 Attila Bo´ta  Powder diffraction apparatus for SAXS measurements J. Appl. Cryst. (2013). 46, 573–576electronic reprint

Modular Tool for Nanostructure Analysis: SAXSess mc 2,

Development of powder diffraction apparatus for small-angle X-ray scattering measurements

A novel type of X-ray collimation system attached to commercial powder diffractometers makes the structural characterization of nanomaterials possible in a wide size range from <0.1 to 100 nm by combination of the small- and wide-angle X-ray scattering techniques. There is no dead interval in the detection between the small- and wide-angle regimes. This device can be attached to any existing `[theta]/[theta]' powder diffractometer, providing a multi-functional small- and wide-angle X-ray scattering/diffraction (SWAXS) apparatus. After proper alignment and adjustment, the device can be removed and re-attached at any time to switch between normal and SWAXS functions

Bota, Attila

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A novel type of X-ray collimation system attached to commercial powder diffractometers makes the structural characterization of nanomaterials possible in a wide size range from &lt;0.1 to 100 nm by combination of the small- and wide-angle X-ray scattering techniques. There is no dead interval in the detection between the small- and wide-angle regimes. This device can be attached to any existing `θ/θ' powder diffractometer, providing a multi-functional small- and wide-angle X-ray scattering/diffraction (SWAXS) apparatus. After proper alignment and adjustment, the device can be removed and re-attached at any time to switch between normal and SWAXS functions.</jats:p

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Development of powder diffraction apparatus for small-angle X-ray scattering measurements

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