ULTRA-SMALL-ANGLE NEUTRON
SCATTERING TECHNIQUE AND USER
COMMUNITY GROWTH IN THE PAST
5 YEARS: A SURVEY
Michael Agamaliana and John M. Carpentera,b
a
SNS, ORNL; b IPNS, ANL
1. Historical Background
It has been shown about 40 years ago that a parallel double-crystal arrangement
(so-called Double-Crystal Diffractometer (DCD) with perfect crystals can be used for
High Q-resolution Small-Angle X-ray/Neutron Scattering studies. However, along with
the high Q-resolution (low Qmin ~ 10-5 Å-1 in case of neutron scattering) conventional
DCDs equipped with single-bounce Si or Ge the crystals had a low Signal-to-Noise Ratio
(SNR) related to the wings of the Darwin reflectivity curve. Those tails created serious
problems for practical application of X-ray and Neutron DCDs for Ultra-Small-Angle
scattering investigations.
In 1965 Bonse and Hart pioneered a new technique at the Cornell University,
which provides dramatic reduction of the Darwin reflectivity curve wings and proved this
technique experimentally for X-ray DCDs. The Bonse-Hart innovation is based on
substituting single-bounce crystals with multi-bounce channel-cut crystals, which provide
the necessary reduction of wings yet preserves the reflectivity in the range of the Darwin
plateau. The Bonse-Hart Ultra-Small-Angle X-ray Scattering (USAXS) instruments
immediately found broad application in many research laboratories worldwide.
The Bonse-Hart X-ray DCDs provided extension of the small-angle X-ray
scattering data into the range of smaller values of Q. Adaptation of the Bonse-Hart
technique for Ultra-Small-Angle Neutron Scattering (USANS) instruments does the same
for SANS. Moreover, the USANS instruments look more attractive than their X-ray
analogs because their Q-resolution is several times higher (narrower Darwin reflectivity
curve) resulting from the smaller values of the neutron coherent scattering lengths
compared to those for X-rays.
The first attempts made by Schwahn & Rauch in the middle of the 1980s to adapt
the Bonse-Hart technique for neutrons had limited success because the authors tried to
use the same crystal design proposed by Bonse & Hart. They did not account for the fact
that neutron absorption of Si, which is mostly in use in the Bonse-Hart DCDs, is about
four orders of magnitude smaller than that for X-rays. Thus, the complete picture of
diffraction from a thick channel-cut crystal including not only the front-face reflection
but also accounting for the back-face reflection must be taken into consideration in case
of neutrons.
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Agamalian, Wignall & Triolo adapted successfully the Bonse-Hart technique for
neutrons at the Oak Ridge National Laboratory in 1997. They changed the design of the
channel-cut crystal by cutting another grove in the long wall and placing a Cd absorber,
which blocked the back-face reflection generating the parasitic scattering. Finally those
modifications improved the SNR for USANS instruments by three orders of magnitude
compared to the value achieved by Schwahn & Rauch. Studying in more detail the
interesting nature of the unusually camel-shaped first back-face reflection they found that
this diffraction signal is extremely sensitive to the ultra-small deformation strain.
Agamalian with co-authors later used this new dynamical diffraction phenomenon, the
so-called Neutron Camel, designing and successfully testing the back-face diffractometer
for the residual stress measurements in thin films.
Two International Awards, the 1999 Arnold O. Beckman Founder Award from
the International Society of Instrumentation and Control (see below) and the 2002 A.
Guinier Prize from the International Union of Crystallography (see below) were given for
this technical breakthrough. The breakthrough to the USANS Q-range was publicly
announced at the Bonse-Hart Session of the XI International Conference on Small-Angle
Scattering, Brookhaven, May 1999. This work was also highlighted in the following
news releases,
“ORNL scientists receive award for neutron research”, Oak Ridger, February 2, 2000.
“Researcher Upgrades ORNL Neutron Scattering Facility”, DOE This Month, April
1999.
“ORAIS Research Participant Develops World’s Best Ultra-Small-Angle Neutron
Scattering Instrument”, Oak Ridge Associated Universities 1998 Annual Report, p. 13.
“Researcher upgrades ORNL neutron scattering facility”, DOE This Month, April 1999.
"ORNL Develops Highly Sensitive Neutron Scattering Instrument", ER News, Vol. 6,
No. 5, September/October 1996.
A flow of interesting structural studies in materials industrial & polymer sciences,
petrology, colloidal chemistry and archeology (see below “USANS Structural Studies”)
followed this dramatic improvement in the USANS experimental technique. The study of
the fractal geometry of rocks (A. Radlinski et al. Phys. Rev. Lett. 82, 3078, 1999) was
published in PRL on April 12, 1999 and after this was immediately highlighted on April
15, 1999 by PRL Focus (see below) and on April 19, 1999 by Academic Press (see
below).
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1999 Arnold O. Beckman Award Poster
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2002 A. Guinier Prize Poster
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2. List of Bonse-Hart USANS Publications
Here we provide a list of publications relating to Bonse-Hart USANS development and
applications.
Articles Related to Bonse-Hart USANS Technique Published Before 1997
There were only two Bonse-Hart Neutron Double-Crystal Diffractometers before
1997. These had Signal-to-Noise Ratio ~ 200 times lower than the X-ray analogs.
1. Schwahn et al. Test of Channel-cut Perfect Crystals for Neutron Small-Angle
Scattering Experiments. Nucl. Instr. Meth. A239, 229, (1985).
2. USANS from Vanadium-Hydrogen Systems. Physica A130/2, 365, (1992).
Articles Related to Bonse-Hart USANS Technique & Application Published in 19972003
The new design of the Si channel-cut crystals developed at ORNL in 1996 improved
the Signal-to-Noise Ration of the Neutron Bonse-Hart Double-Crystal
Diffractometers by ~ 1000 times making performance of these instruments even
better that the classical USAXS cameras.
Instrument & software development
1. Agamalian et al. Optimization of a Bonse-Hart Ultra-Small Angle Neutron Scattering
Facility by Eliminating the Rocking Curve Wings. J.Appl.Cryst., 30, 345, (1997).
2. Drews et al. Development of a Thermal-Neutron Double-Crystal Diffractometer for
USANS at NIST, Physica B, 241-243, 189, (1998).
3. Agamalian et al. Recent Developments in Ultra-Small-Angle Neutron Scattering
Techniques, Neutron News, 9, 24, (1998).
4. Agamalian et al. Surface-Induced Parasitic Scattering in Bonse-Hart Double Crystal
Diffractometers, Appl. Cryst., 31, 235, (1998).
5. Agamalian et al. Time-of-Flight Ultra-Small-Angle Neutron Scattering Instrument
for the SNS, with Proceedings of SPIE, 4785, 134-142, (2002).
6. Barker et al. Double-Crystal Diffractomter. Instrument Design Report. NIST, 5/98,
45 pages.
7. Takahashi et al. USANS Instrument at C1-3 in JRR-3M. J. Phys. Chem. of Solids,
60, 1591, (1999).
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8. Bellmann et al. Performance of a DCD with different Channel-Cut Perfect Si
Crystals. Physica B, 276, 124, (2000).
9.
Borbely et al. Resolution of the USANS Diffractometer at the FRJ-2 Research
Reactor in Juelich. Physica B, 276, 138, (2000).
10. Hainbuchner et al. The New High Resolution USANS Instrument at the High-Flux
Reactor in Grenoble. J. Appl. Cryst., 33, 851, (2000).
11. Triemer et al. Development of a Tunable Channel-cut Crystals. Phys. Lett. 289A,
151, (2001).
12. Villa et al. Optimization of a Crystal Design for a Bonse-Hart Camera. J. Appl.
Cryst. 36, 769, (2003).
13. Carpenter et al. Time-of-Flight Implementation of an USANS Instrument.
J.Appl.Cryst. 36, 763, (2003).
14. Carpenter et al. Time-of-Flight Implementation of an USANS Instrument.
J.Appl.Cryst. 36, 763, (2003).
15. Agamalian et al. Recent Development in USANS Techniques. Neutron News, 9,
24, (1998).
16. Wagh et al. SUSANS (Super USANS) with Polarized Neutrons, BENSC
Experimental Report, January, (2003).
17. Littrell & Wai Tung Lee. A Method for Polarization Control and Analysis on
Bonse-Hart DCD USANS Instruments, to be published in Physica B (2003).
Dynamical Diffraction & Satellite Technique
1. Agamalian et al. Back-Face Bragg Diffraction from a Perfect and Ultra-Lightly
Deformed Thick Crystal, Phys. Rev. Lett., 81, 602, (1998).
2. Agamalian et al. A New Dynamical Diffraction Effect “Neutron Camel”, Neutron
News, 10, 24, (1999).
3.
Agamalian et al. Dynamical Neutron-Scattering Measurements of Residual Stress in
a Si Crystal Coated With a Thin Film, Phys. Rev. B, 64, 161402, (2001).
4. Agamalian et al. A New Dynamical Diffraction-Based Technique of the Residual
Stress Measurements in Thin Films, Appl. Phys. A, 74 [Suppl 1], S1686, (2002).
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5. Wagh et al. Bonse-Hart Angular Profiles Realized for Multiply Bragg Reflected
Neutrons. Phys. Rev. Lett. 87, 12, (2001).
6.
Aizawa et al. Attempt to Refrigerate Si Crystal Optical Component on a DCD II,
JAERI-Review, 107, (2002-006).
USANS Structural Studies
1. Matsuoka et al. Ultra-Small-Angle Neutron Scattering Study of Colloidal Alloys,
Langmuir, 15, 293, (1999).
2. Agamalian et al.Phase Behaviour of Blends of Linear and Branched Polyethylenes on
Micron Length-Scales via Ultra-Small-Angle Neutron Scattering, Macromolecules,
32, 3093, (1999).
3. Radlinski et al. The fractal geometry of rocks, Phys. Rev. Lett., 82, 3078, (1999).
4. Radlinski et al. The fractal geometry of rocks, ILL Annual Report, Grenoble, 36,
(1999).
5. Schaefer et al. Multilevel Structure of Reinforcing Silica and Carbon. J Appl. Cryst.,
33, 587, (2000).
6. Triolo et al. Fractal Approach in Petrology: Combining USANS, SANS and IANS,
J. Appl. Cryst., 33, 863, (2000).
7. Agamalian et al. Phase Behaviour of Blends of Linear and Branched Polyethylenes
on Micron Length-Scales via Ultra-Small-Angle Neutron Scattering, J. Appl. Cryst.,
33, 843, (2000).
8. Radlinski et al. The fractal microstructure of ancient sedimentary rocks, J. Appl.
Cryst., 33, 860, (2000).
9. You-Yeon Won et al. Segment Distribution of the Micellar Brushes of
Poly(ethylene oxide) via Small-Angle Neutron Scattering, J. Phys. Chem. B, 104,
7134, (2000).
10. Harada et al. The Structure of Colloiday Alloy Crystals Revealed by Ultra-SmallAngle Neutron Scattering, Colloids & Surfaces A, 190, 17-24, (2001).
11. Bhatia et al. Scattering of Disklike Particle Suspensions: Evidence for Repulsive
Interactions and Large Length Scale Structure from Static Light Scattering and
USANS. Langmuir, 19, 532, (2003).
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12. Schneider et al. Responsive Hydrogels from the Intramolecular Folding and
Self-Assembly of a Designed Peptide. J. Am. Chem. Soc., 124, 15030, (2002).
13. Aizawa et al. Morphology of Ni-base superalloys via very small-angle neutron
scattering technique. J. Appl. Cryst. 33, 847, (2000).
14. Matsuoka et al. Ultra-small-angle X-ray and Neutron Scattering Studies on Colloidal
Crystals. J. Appl. Cryst. 33, 855, (2000).
15. Matsuoka et al. USANS Study of Colloidal Alloys. 1. Contrast Variation
Experiments for H/D Mixtures of Polystyrene Latices in H2O/D2O. Langmuir, 15,
293, (1999).
16. Muzny et al. USANS Study of the Restructuring of Sheared Colloidal Silica Gels.
J. Phys. Condensed Matter, 11, L295, (1999).
17. Wagh et al. Bonse-Hart Angular Profiles Realized for Multiply Bragg Reflected
Neutrons. Phys. Rev. Lett. 87, 12, (2001).
18. Hainbucher et al. Scattering Studies of Large Scale Structures at the USANS
Instrument S18. Physica A304, 220, (2002).
19. Schneider et al. Responsive Hydrogels from the Intramolecular Folding and Selfassambly of a Designed Peptide. J. American Chemical Soc. 124, 15030, (2002)
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20. Triemer et al. Observation of Edge Refraction in USANS. Phys. Lett. A305, 87,
(2002).
21. Jericha et al. USANS studies of Artificial Lattices. J. Appl. Cryst. 36, 778, (2003).
22. Ryukhtin et al. Comparative Study of Porosity in 3Y-TZP Superplastic Ceramics by
USANS and EM Image Analysis. J. Appl. Cryst. 36, 478, (2003).
23. Villa et al. Optimization of a Crystal Design for a Bonse-Hart Camera. J. Appl.
Cryst. 36, 769, (2003).
24. Aizawa et al. Characterization of Single-Crystal Ni-base superalloy CMSX-4 with
creep damage. JAERI-Review, 1999-003, p. 93.
25. Hashimoto et al. Scattering Studies on Hierarchical Structures of Rubber/Filter
Systems. JAERI-Review, 2001-005, p. 17.
26. Hashimoto et al. Scattering Studies on Hierarchical Structures of Rubber/Filter
Systems. JAERI-Review, 2002-006, p. 21.
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27. Koizumi et al. Fractal Structure of a Poly(N-isopropylacrylamide) Gel. Studied by
Small-Angle Neutron Scattering over Q-Range from 10-5 to 0.1 Å. JAERI-Review,
2000-005, p. 8.
28. Izumi et al. PNO Study on Bovine Serum Albumin Gels 2. JAERI-Review,
2000-005, p. 15.
29. Izumi et al. PNO Study on Bovine Serum Albumin Gels. JAERI-Review,
1999-003, p. 27.
30. Steriotis et al. USANS Study of Nano-ceramic Semiconductors, BENSC
Experimental Report, January, (2001).
31. Schwahn Long- and Short-range Spatial Inhomogenuities in Porous Matrices of
Vycor Glass and Aerogels, FRJ-2 Experimental Reports (2002), p. 143.
32. Baron et al. Ultra-Small Angle Neutron Scattering on S18. ILL Annual Report
(2000).
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3. International Meetings related to the BonseHart Technique and Application
Here we provide information on recent international meetings concerned with Bonse-Hart
diffraction.
IConUSAS Workshop
In July 2003 the first Workshop of International Consortium on Ultra-Small-Angle
Scattering convened in Oak Ridge, TN. Following are the Workshop Announcement and
Program.
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IConUSAS Workshop Program
July 9
Registration. Coffee & Snacks (7:30 – 8:30 AM)
1. Introductory session. (8:30 AM)
Chair: Roberto Triolo
1. Ian Anderson “The SNS Experimental Facilities” (10 min)
2. Herbert Mook “New Neutron Scattering Opportunities at the Upgraded HFIR”
(10 min)
3. Lee Magid “Joint Institute of Neutron Science” (10 min)
4. Michael Agamalian “The Bonse-Hart Technique for Neutrons ” (20 min)
5. Kenneth Littrell “A Brief History of the Wing Problem” (20 min)
6. Willem Bertram “The Effects of Multiple Scattering on the Analysis of USANS
Data” (20 min)
7. Jan Saroun "SASProFit - Program for USANS Data Evaluation" (20 min)
Coffee break (10:20 AM – 10:40 AM)
2. Design and Application of the Existing USANS Instruments (10:40 AM)
Chair: Peter Timmins
8. Dietmar Schwahn “The First Experiments with the Bonse-Hart Channel-cut
Crystals. Application of the USANS Instrument at FRJ-2 in Jülich (20 min)
9. John Barker “Design and Application of the USANS Instrument at NIST” (20
min)
10. Matthias Baron “Design and Applications of the S18-USANS Instrument at ILL”
(20 min)
11. Mario Villa “Optimization of the USANS Instruments at ILL, PSI and in Vienna”
(20 min)
Lunch break (12:00 PM – 1: 30 PM)
3. New Projects of USANS and TOF-USANS Instruments (1:30 PM)
Chair: Jack Carpenter
12. Michael Agamalian “The TOF-USANS Instrument for SNS” (20 min)
13. Kazuya Aizawa “The TOF-USANS Instrument for Japanese SNS” (20 min)
14. Helmut Kaiser “Neutron flux computation for various pre-monochromators for a
proposed USANS at HFIR” (20 min)
4. Discussion of the SNS TOF-USANS Project (2:30 PM – 4:10 PM)
Chair: Michael Agamalian
Coffee break (4:10 PM – 4:30 PM)
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5. Alternative (none Bonse-Hart) Ultra- and Very-Small-Angle Neutron
Scattering Techniques (4:30 – 5:30 PM)
Chair: George Wignall
15. Ronald Gähler “Equipping a SANS Instrument with an USANS option” (20 min)
16. Timofei Krouglov "Phase Transitions in Colloidal Crystals Studied with the SpinEcho SANS"
(20 min)
17. Daniel Clemens “Very Small-Angle Neutron Scattering Instrument for
BENSC/HMI”
(20 min)
Cash Bar (7:00)
Conference dinner (7:30 PM)
Welcome from the SNS Administration
IConUSAS Awards from Roberto Triolo
July 10
Coffee & Snacks (8:00 – 8:30 AM)
6. Organizing Session “IConUSAS Consortium” (8:30 AM – 9:00 AM)
Chair: Jack Carpenter
7. USANS Application in Materials & Polymer Science (9:00 AM)
Chair: Kenneth Littrell
18. George Wignall “USANS Study of Bends of Linear and Branched Polyethylene”
(20 min).
19. Yuri Melnichenko “USANS and SANS Study of Porosity in Vycor Glass” (20
min)
20. Dale Schaefer “Multilevel Structure of Reinforcing Silica and Carbon” (20 min)
21. Surita R. Bhatia “Large Length-Scale Structure in Laponite Gels and Block
Polyelectrolyte
Solutions” (20 min)
22. Darrin Pochan “Nano- and Microporous Hydrogels Constructed via Peptide Selfassembly”
(20 min)
Coffee break (10:40 AM – 11:00 AM)
8. X-ray Session (11:00 AM)
Chair: John Barker
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23. Toshio Takahashi “Application of the Darwin Theory for Structural Study of
Surface Layers”
(20 min)
24. Thomas Reiker “USAXS on a Rotating Anode Source” (20 min)
25. Andrew Allen “The UNICAT Ultra-Small-Angle X-ray Double-Crystal
Diffractometer at the Advanced Photon Source” (20 min)
26. Theyencheri Narayanan “USAXS” Studies at ESRF” (20 min)
Lunch break (12:20 – 2:00 PM)
8. Application of USANS in Petrology, Archaeometry, Natural & Industrial
Sciences
(2:00 PM)
Chair: Helmut Rauch
27. Andrzej Radlinski “USANS & SANS Study of Sedimentary Rocks” (20 min)
28. Roberto Triolo “Application of the USANS Technique in Natural Sciences and
Archaeometry” (20 min)
29. Willem Bertram “Results from Time Resolved USANS Measurements on
Hydrating Cement Pastes” (20 min)
Coffee break (3:00 PM – 3:20 PM)
9. “Non-Conventional” Application of the Bonse-Hart DCDs (3:20 PM)
Chair: Sam Werner
30. Helmut Rauch “USANS Study of Artificial Structures” (20 min)
31. Wolfgang Treimer “A Tuneable Bonse-Hart Camera. Tomographic Imaging With
a Bonse-Hart Camera (30 min)
32. Christine Rehm “Residual Stress & Reflectivity Measurements on Ni/Ti Multilayer films”
(20 min)
Coffee break (4:20 PM – 4:40 PM)
10. Brake out Session “US-Japan Collaboration on USANS” (time is under
discussion)
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XII International Conference on SAS
In August 2002 the major SAS conference sponsored by the International Union of
Crystallography took place in Venice, Italy. The program included nearly a dozen
presentations on USANS technique and applications. Below we list the USANS/USAXS
presentations.
M. Agamalian RECENT DEVELOPMENTS IN THE USANS AND SATTELITE
TECHNIQUE
J. Carpenter CONCEPT FOR A PULSED-SOURCE IMPLEMENTATION OF
A TIME-OF-FLIGHT USANS INSTRUMENT
M. Villa OPTIMIZATION OF A CRYSTAL DESIGN FOR A BONSE-HART
CAMERA
C. Livet USAXS: CONDITONS LIMITS AND RESULTS IN SPECKLE
EXPERIMENTS
M. Jericha USANS STUDIES OF ARTIFICIAL LATTICES
R. Triolo REVEALING FRACTAL PATTERNS BY COMBINED USANS/SANS
T. Narayanan USAXS STUDIES OF ATTRACTIVE COLLOIDAL GLASS
TRANSITION
S. Bhatia STRUCTURE OF PEO-PPO-PEO GELS IN MAMMALIAN CELL
MEDIUM FOR TISSUE ENGINEERING APPLICATIONS
T. Sabine AN UltraSANS STUDY OF SYNROC
D. Schaefer STRUCTURE OF CARBON NANOTUBES
D. Schaefer EFFECT OF DRYING ON THE STRUCTURE AND DISPERSION OF
PRECIPITATED SILICA IN ORGANIC RUBBER
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XII International Conference on SAS
The 1999 SAS conference sponsored by the International Union Of Crystallography took
place in May 17-20, 1999, BNL, USA. At this conference M. Agamalian announced the
breakthrough to Ultra-Small-Q diffraction. Below we list the presentations at the BonseHart USAS session.
M. Agamalian BREAKTHROUGH TO µm-SCALE RANGE OF NEUTRON
DIFFRACTION STRUCTURAL ANALYSIS (ULTRA-SMALL
ANGLES)
G. D. Wignall PHASE BEHAVIOR OF BLENDS OF LINEAR AND BRANCHED
POLYETHYLENES ON MICRON LENGTH-SCALES VIA USANS
K. Aizawa MORPHOLOGY OF Ni-BASE SUPPERALLOYSVIA VERY
SMALL-ANGLE NEUTRON SCATTERING TECHNIQUE
J. Barker A NEUTRON BONSE-HART DIFFRACTOMETER AT NIST
A. Kroupa THE NEW HIGH RESOLUTION USANS INSTRUMENT AT HIGH FLUX
REACTOR IN GRENOBLE
M. Lin USANS APPLICATION ON ENGINE OILS
J.S. Lin RECENT APPLICATION AND PERFORMANCE OF THE ORNL USANS
FACILITY
H. Matsuoka USAXS AND USANS STUDY OF COLLOIDAL CRYSTALS
A. Radlinski THE FRACTAL MICROSTRUCTURE OF PEROLIFEROUS
SEDIMENTARY ROCKS
T. Sabine ANALYSIS OF USANS DATA FROM HYDRATED CEMENT PASTE
R. Triolo FRACTAL APPROACH IN PETROGRAPHY: COMBINING USANS, SANS
AND IANS
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