A new small‐angle X‐ray scattering set‐up on the crystallography beamline I711 at MAX‐lab

A small‐angle X‐ray scattering (SAXS) set‐up has recently been developed at beamline I711 at the MAX II storage ring in Lund (Sweden). An overview of the required modifications is presented here together with a number of application examples. The accessible q range in a SAXS experiment is 0.009–0.3 Å^?1 for the standard set‐up but depends on the sample‐to‐detector distance, detector offset, beamstop size and wavelength. The SAXS camera has been designed to have a low background and has three collinear slit sets for collimating the incident beam. The standard beam size is about 0.37 mm × 0.37 mm (full width at half‐maximum) at the sample position, with a flux of 4 × 10¹⁰ photons s^?1 and λ = 1.1 Å. The vacuum is of the order of 0.05 mbar in the unbroken beam path from the first slits until the exit window in front of the detector. A large sample chamber with a number of lead‐throughs allows different sample environments to be mounted. This station is used for measurements on weakly scattering proteins in solutions and also for colloids, polymers and other nanoscale structures. A special application supported by the beamline is the effort to establish a micro‐fluidic sample environment for structural analysis of samples that are only available in limited quantities. Overall, this work demonstrates how a cost‐effective SAXS station can be constructed on a multipurpose beamline.     

Time-resolved SAXS measurements facilitated by online HPLC buffer exchange

Small‐angle X‐ray scattering (SAXS) is a powerful technique to structurally characterize biological macromolecules in solution. Heterogeneous solutions are inherently challenging to study. However, since SAXS data from ideal solutions are additive, with careful computational analysis it may be possible to separate contributions from individual species present in solution. Hence, time‐resolved SAXS (TR‐SAXS) data of processes in development can be analyzed. Many reported TR‐SAXS results are initialized by a sudden change in buffer conditions facilitated by rapid mixing combined with either continuous or stopped flow. In this paper a method for obtaining TR‐SAXS data from systems where the reaction is triggered by removal of a species is presented. This method is based on fast buffer exchange over a short desalting column facilitated by an online HPLC (high‐performance liquid chromatography) connected to the SAXS sample cell. The sample is stopped in the sample cell and the evolving reaction is followed. In this specific system the removal of phenol initiates a self‐association process of long‐acting insulin analogues. For this experiment, data were collected in time series while varying concentrations. The method can be generally applied to other systems where removal of a species or other changes in experimental conditions trigger a process.     

Simultaneous small‐ and wide‐angle scattering at high X‐ray energies

Combined small‐ and wide‐angle X‐ray scattering (SAXS/WAXS) is a powerful technique for the study of materials at length scales ranging from atomic/molecular sizes (a few angstroms) to the mesoscopic regime (～1 nm to ～1 µm). A set‐up to apply this technique at high X‐ray energies (E > 50 keV) has been developed. Hard X‐rays permit the execution of at least three classes of investigations that are significantly more difficult to perform at standard X‐ray energies (8–20 keV): (i) in situ strain analysis revealing anisotropic strain behaviour both at the atomic (WAXS) as well as at the mesoscopic (SAXS) length scales, (ii) acquisition of WAXS patterns to very large q (>20 Å^?1) thus allowing atomic pair distribution function analysis (SAXS/PDF) of micro‐ and nano‐structured materials, and (iii) utilization of complex sample environments involving thick X‐ray windows and/or samples that can be penetrated only by high‐energy X‐rays. Using the reported set‐up a time resolution of approximately two seconds was demonstrated. It is planned to further improve this time resolution in the near future.     

Status of PRESS-MAG-O: The experimental apparatus to probe materials and phenomena under extreme conditions at Frascati

In this contribution we up-to-date the status of the PRESS-MAG-O device, a new instrument under commissioning at the INFN designed to perform magnetic and spectroscopic experiments on samples under extreme conditions. The system has been designed to work at SINBAD, the IR synchrotron radiation beamline operational at DAΦNE. The instrument, that is the result of a significant R&D, will allow performing concurrent high harmonic ac magnetic susceptibility measurements and magneto-optic experiments on a sample under high pressure, with a variable DC magnetic field in a wide temperature range. The vacuum vessel has been designed with four crossing windows to allow optical measurements in the transmission geometry on the sample loaded inside a Diamond Anvil Cell. A new superconducting miniaturized micro-SQUID gradiometer has been also developed to detect the low magnetic signal of the sample and a customized optical system has also been designed to perform IR synchrotron radiation experiments.     

Thorough small‐angle X‐ray scattering analysis of the instability of liquid micro‐jets in air

Liquid jets are of interest, both for their industrial relevance and for scientific applications (more important, in particular for X‐rays, after the advent of free‐electron lasers that require liquid jets as sample carrier). Instability mechanisms have been described theoretically and by numerical simulation, but confirmed by few experimental techniques. In fact, these are mainly based on cameras, which is limited by the imaging resolution, and on light scattering, which is hindered by absorption, reflection, Mie scattering and multiple scattering due to complex air/liquid interfaces during jet break‐up. In this communication it is demonstrated that synchrotron small‐angle X‐ray scattering (SAXS) can give quantitative information on liquid jet dynamics at the nanoscale, by detecting time‐dependent morphology and break‐up length. Jets ejected from circular tubes of different diameters (100–450 µm) and speeds (0.7–21 m s^?1) have been explored to cover the Rayleigh and first wind‐induced regimes. Various solvents (water, ethanol, 2‐propanol) and their mixtures have been examined. The determination of the liquid jet behaviour becomes essential, as it provides background data in subsequent studies of chemical and biological reactions using SAXS or X‐ray diffraction based on synchrotron radiation and free‐electron lasers.     

Small‐angle solution scattering using the mixed‐mode pixel array detector

Solution small‐angle X‐ray scattering (SAXS) measurements were obtained using a 128 × 128 pixel X‐ray mixed‐mode pixel array detector (MMPAD) with an 860 µs readout time. The MMPAD offers advantages for SAXS experiments: a pixel full‐well of >2 × 10⁷ 10 keV X‐rays, a maximum flux rate of 10⁸ X‐rays pixel^?1 s^?1, and a sub‐pixel point‐spread function. Data from the MMPAD were quantitatively compared with data from a charge‐coupled device (CCD) fiber‐optically coupled to a phosphor screen. MMPAD solution SAXS data from lysozyme solutions were of equal or better quality than data captured by the CCD. The read‐noise (normalized by pixel area) of the MMPAD was less than that of the CCD by an average factor of 3.0. Short sample‐to‐detector distances were required owing to the small MMPAD area (19.2 mm × 19.2 mm), and were revealed to be advantageous with respect to detector read‐noise. As predicted by the Shannon sampling theory and confirmed by the acquisition of lysozyme solution SAXS curves, the MMPAD at short distances is capable of sufficiently sampling a solution SAXS curve for protein shape analysis. The readout speed of the MMPAD was demonstrated by continuously monitoring lysozyme sample evolution as radiation damage accumulated. These experiments prove that a small suitably configured MMPAD is appropriate for time‐resolved solution scattering measurements.     

Biomolecular solution X-ray scattering at the National Synchrotron Light Source

In recent years there has been a growing interest in the application of X-ray scattering techniques to biomolecules in solution. At NSLS, a new undulator-based beamline, X9, has been constructed to address the oversubscribed user demand for X-ray scattering. Beamline X9 has the capability to perform small/wide-angle X-ray scattering (SAXS/WAXS) all in one single instrument. This is accomplished by utilizing a vacuum sample/detector chamber that is an integral part of the SAXS scattering flight path. This vacuum chamber allows a WAXS detector to be positioned at a close distance from the sample, while not interfering with scattered X-rays at small angles from reaching the SAXS detector. A regular training program, the X9 workbench, has also been established to allow users to become familiar with beamline X9 for solution X-ray scattering.     

A 1800 K furnace designed for in situ synchrotron microtomography

A radiation furnace that covers the temperature range from room temperature up to 1800 K has been designed and constructed for in situ synchrotron microtomography. The furnace operates under a vacuum or under any inert gas atmosphere. The two 1000 W halogen heating lamps are water‐ and air‐cooled. The samples are located at the focus of these lamp reflectors on a rotary feedthrough that is connected to a driving rotation stage below the furnace. The X‐ray beam penetrates the furnace through two X‐ray‐transparent vacuum‐sealed windows. Further windows can be used for temperature control, sample changing and gas inflow and outflow.     

Mechanical Behavior of Bulk Poly(Ethylene Terephthalate) Subjected to Simple Shear

Abstract

Mechanical behavior of bulk semicrystalline poly(ethylene terephthalate) (PET) processed through simple shear is investigated. The equal channel angular extrusion (ECAE) process was used to achieve the simple shear condition. The PET samples were processed in one and two ECAE passes in the same direction, with the sample rotated 180° about the extrusion axis for the second pass. Microstructural features at the nanometer and micrometer scales were studied by small‐angle x‐ray scattering (SAXS) and scanning electron microscopy (SEM). SAXS results showed that at the nanometer scale, two types of lamellar orientations are induced in both samples, but with different extents of orientation. In the ECAE‐oriented PET structures on the micrometer scale, as revealed by SEM, are well‐defined macrofibrils. However, the fibrillar structures in the sample extruded once are more oriented than those in the sample extruded twice. Fractography investigations suggest that the ECAE‐induced fibrillar structure and stretched amorphous chains are responsible for the change in mechanical properties.     

Upgrade of MacCHESS facility for X‐ray scattering of biological macromolecules in solution

X‐ray scattering of biological macromolecules in solution is an increasingly popular tool for structural biology and benefits greatly from modern high‐brightness synchrotron sources. The upgraded MacCHESS BioSAXS station is now located at the 49‐pole wiggler beamline G1. The 20‐fold improved flux over the previous beamline F2 provides higher sample throughput and autonomous X‐ray scattering data collection using a unique SAXS/WAXS dual detectors configuration. This setup achieves a combined q‐range from 0.007 to 0.7 Å^?1, enabling better characterization of smaller molecules, while opening opportunities for emerging wide‐angle scattering methods. In addition, a facility upgrade of the positron storage ring to continuous top‐up mode has improved beam stability and eliminated beam drift over the course of typical BioSAXS experiments. Single exposure times have been reduced to 2 s for 3.560 mg ml^?1 lysozyme with an average quality factor I/σ of 20 in the Guinier region. A novel disposable plastic sample cell design that incorporates lower background X‐ray window material provides users with a more pristine sample environment than previously available. Systematic comparisons of common X‐ray window materials bonded to the cell have also been extended to the wide‐angle regime, offering new insight into best choices for various q‐space ranges. In addition, a quantitative assessment of signal‐to‐noise levels has been performed on the station to allow users to estimate necessary exposure times for obtaining usable signals in the Guinier regime. Users also have access to a new BioSAXS sample preparation laboratory which houses essential wet‐chemistry equipment and biophysical instrumentation. User experiments at the upgraded BioSAXS station have been on‐going since commissioning of the beamline in Summer 2013. A planned upgrade of the G1 insertion device to an undulator for the Winter 2014 cycle is expected to further improve flux by an order of magnitude.     

Characterization of nanosized partly crystalline photocatalysts

A thorough analysis of nanosized partly crystalline photocatalysts has been carried out. X-ray diffraction (XRD), Small angle X-ray Scattering (SAXS), Scanning electron microscope (SEM), and BET measurements have been applied to study the particle properties of different photocatalysts. The study permitted the determination of absolute crystallinity of partly and fully crystalline photocatalysts by XRD. The absolute crystallinity was determined with CaF₂ as a reference. SAXS measurements were used to study the morphology and to determine the primary particle size of the investigated photocatalysts. The study showed that the commercially available photocatalyst Hombikat UV100 consisted of a great fraction of amorphous material whereas Degussa P25 was found to be almost crystalline. A homemade sample was found to be 63% crystalline anatase and 37% amorphous. The study also revealed that there was a deviation between the primary particle size and the crystal size for the partly crystalline samples caused by the amorphous fraction; however, the fully crystalline Degussa P25 had agreement between the primary particle size and the crystal size.     

Performance on absolute scattering intensity calibration and protein molecular weight determination at BL16B1, a dedicated SAXS beamline at SSRF

The optical system and end‐station of bending‐magnet beamline BL16B1, dedicated to small‐angle X‐ray scattering (SAXS) at the Shanghai Synchrotron Radiation Facility, is described. Constructed in 2009 and upgraded in 2013, this beamline has been open to users since May 2009 and supports methodologies including SAXS, wide‐angle X‐ray scattering (WAXS), simultaneous SAXS/WAXS, grazing‐incidence small‐angle X‐ray scattering (GISAXS) and anomalous small‐angle X‐ray scattering (ASAXS). Considering that an increasing necessity for absolute calibration of SAXS intensity has been recognized in in‐depth investigations, SAXS intensity is re‐stated according to the extent of data processing, and the absolute intensity is suggested to be a unified presentation of SAXS data in this article. Theory with a practical procedure for absolute intensity calibration is established based on BL16B1, using glass carbon and water as primary and secondary standards, respectively. The calibration procedure can be completed in minutes and shows good reliability under different conditions. An empirical line of scale factor estimation is also established for any specific SAXS setup at the beamline. Beamline performance on molecular weight (MW) determination is provided as a straightforward application and verification of the absolute intensity calibration. Results show good accuracy with a deviation of less than 10% compared with the known value, which is also the best attainable accuracy in recent studies using SAXS to measure protein MW. Fast MW measurement following the demonstrated method also enables an instant check or pre‐diagnosis of the SAXS performance to improve the data acquisition.     

A dedicated small‐angle X‐ray scattering beamline with a superconducting wiggler source at the NSRRC

At the National Synchrotron Radiation Research Center (NSRRC), which operates a 1.5 GeV storage ring, a dedicated small‐angle X‐ray scattering (SAXS) beamline has been installed with an in‐achromat superconducting wiggler insertion device of peak magnetic field 3.1 T. The vertical beam divergence from the X‐ray source is reduced significantly by a collimating mirror. Subsequently the beam is selectively monochromated by a double Si(111) crystal monochromator with high energy resolution (ΔE/E? 2 × 10^?4) in the energy range 5–23 keV, or by a double Mo/B₄C multilayer monochromator for 10–30 times higher flux (～10¹¹ photons s^?1) in the 6–15 keV range. These two monochromators are incorporated into one rotating cradle for fast exchange. The monochromated beam is focused by a toroidal mirror with 1:1 focusing for a small beam divergence and a beam size of ～0.9 mm × 0.3 mm (horizontal × vertical) at the focus point located 26.5 m from the radiation source. A plane mirror installed after the toroidal mirror is selectively used to deflect the beam downwards for grazing‐incidence SAXS (GISAXS) from liquid surfaces. Two online beam‐position monitors separated by 8 m provide an efficient feedback control for an overall beam‐position stability in the 10 µm range. The beam features measured, including the flux density, energy resolution, size and divergence, are consistent with those calculated using the ray‐tracing program SHADOW. With the deflectable beam of relatively high energy resolution and high flux, the new beamline meets the requirements for a wide range of SAXS applications, including anomalous SAXS for multiphase nanoparticles (e.g. semiconductor core‐shell quantum dots) and GISAXS from liquid surfaces.     

Sound velocities of compressed Fe3C from simultaneous synchrotron X‐ray diffraction and nuclear resonant scattering measurements

The applications of nuclear resonant scattering in laser‐heated diamond anvil cells have provided an important probe for the magnetic and vibrational properties of ⁵⁷Fe‐bearing materials under high pressure and high temperature. Synchrotron X‐ray diffraction is one of the most powerful tools for studying phase stability and equation of state over a wide range of pressure and temperature conditions. Recently an experimental capability has been developed for simultaneous nuclear resonant scattering and X‐ray diffraction measurements using synchrotron radiation. Here the application of this method to determine the sound velocities of compressed Fe₃C is shown. The X‐ray diffraction measurements allow detection of microscale impurities, phase transitions and chemical reactions upon compression or heating. They also provide information on sample pressure, grain size distribution and unit cell volume. By combining the Debye velocity extracted from the nuclear resonant inelastic X‐ray scattering measurements and the structure, density and elasticity data from the X‐ray diffraction measurements simultaneously obtained, more accurate sound velocity data can be derived. Our results on few‐crystal and powder samples indicate strong anisotropy in the sound velocities of Fe₃C under ambient conditions.     

Studies of intrawall porosity in the hexagonally ordered mesostructures of SBA-15 by small angle X-ray scattering and nitrogen adsorption

Ordered mesoporous silicas (OMSs) such as SBA-15 (p6mm symmetry group) synthesized in the presence of block copolymers containing poly(ethylene oxide) blocks possess irregular complementary pores in the walls of ordered mesopores. The X-ray scattering caused by this complementary porosity contributes to the background of the SAXS patterns. This work shows the possibility of using the SAXS data for the study of intrawall channels interconnecting ordered cylinders in SBA-15. The proposed SAXS analysis was tested by using a series of SBA-15 samples obtained at different temperatures of hydrothermal treatment (from 60 to 180 °C). The structural modelling of the SAXS patterns recorded for a series of SBA-15 samples was performed by using the continuous density function (CDF) technique in combination with the derivative difference minimization (DDM) method of full-profile refinement. This method is well suited for extraction of the background curves from the SAXS patterns. The resulting smooth background curves were analyzed by the well-known method in the SAXS theory used for evaluation of heterogeneity distributions, which in this case characterize the intrawall complementary porosity. A relatively good agreement has been observed between the data obtained by SAXS and nitrogen adsorption analysis. The SAXS analysis is sufficiently sensitive for examination of heterogeneous microporosity in SBA-15 materials. The average diameter of intrawall pores for the SBA-15 sample obtained at 60 °C was only about 1.4 nm. However, this diameter increased with the increasing temperature of hydrothermal treatment; namely, it was 1.5, 1.8, 2.6, 2.6, 3.5 and 5.2 nm for the SBA-15 samples hydrothermally treated at 80, 100, 120, 140, 160 and 180 °C, respectively.     

Colloidal Crystals of NaYF4 Upconversion Nanocrystals Studied by Small‐Angle X‐Ray Scattering (SAXS)

Spherical NaYF₄ upconversion nanocrystals with mean radii of about 5 and 11 nm are observed to form colloidal crystals, i.e., 3D assemblies of the particles with long‐range order. The colloidal crystals of the larger particles form directly in solution when dispersions of the particles in toluene are stored at room temperature for several weeks. Crystallization of the smaller particles takes place when their dispersions in hexane are slowly dried at elevated temperatures. The formation and the structure of the colloidal crystals are studied by small‐angle X‐ray scattering (SAXS). SAXS measurements show that the smaller as well as the larger particles assemble into a face‐centered cubic lattice with unit cell dimensions of a = 18.7 nm and a = 35.5 nm, respectively. The SAXS data also show that the particles in the colloidal crystals still bear a layer of oleic acid on their surfaces. The thickness of this layer is 1.5–1.8 nm, as determined by comparing the unit cell dimensions of the colloidal crystals with the mean particle sizes. The latter could be very precisely determined from the distinct oscillations observed in the SAXS data of dilute colloidal dispersions of the nanocrystals.     

The measurement of optical constants of volatile liquids

An experimental system which was devised to measure the optical constants of volatile liquids has been used to find the optical constants of two freons. The experimental arrangement is an adaptation of a free liquid surface reflectometer described in another paper from this group. In this case, however, the liquid under test and the reference liquid are not exposed to the atmosphere but are contained by cells which have infrared transmitting windows. Optical constants, n(λ) and where applicable k(λ), for two volatile liquid samples trichlorofluoromethane and 1,1,2 trichlorotrifluoroethane, which gave large absorption peaks in the infrared, have been found using the closed cell technique in the 2–13 μm wavelength region.     

利用x射线小角散射技术研究微晶硅薄膜的微结构

采用x射线小角散射（SAXS）技术研究了由射频等离子体增强化学气相沉积（rf-PECVD）、 热丝化学气相沉积(HWCVD)和等离子体助热丝化学气相沉积(PE-HWCVD)技术制备的微晶硅（ μc-Si:H）薄膜的微结构.实验发现，在相同晶态比的情况下，PECVD沉积的μc-Si:H薄膜微 空洞体积比小，结构较致密，HWCVD沉积的μ-Si:H薄膜微空洞体积比大，结构较为疏松，PE -HWCVD沉积的μc-Si:H薄膜，由于等离子体的敲打作用，与HWCVD样品相比，微结构得到明 显改善.采用HWCVD二步法和PE-HWCVD加适量Ar离子分别沉积μc-Si:H薄膜，实验表明，微结 构参数得到了进一步改善.45°倾角的SAXS测量显示，不同方法制备的μc-Si:H薄膜中微空 洞分布都呈各向异性.红外光谱测量也证实了SAXS的结果. 关键词： 微晶硅薄膜 微结构 微空洞 x射线小角散射     

A reaction cell with sample laser heating for in situ soft X‐ray absorption spectroscopy studies under environmental conditions

A miniature (1 ml volume) reaction cell with transparent X‐ray windows and laser heating of the sample has been designed to conduct X‐ray absorption spectroscopy studies of materials in the presence of gases at atmospheric pressures. Heating by laser solves the problems associated with the presence of reactive gases interacting with hot filaments used in resistive heating methods. It also facilitates collection of a small total electron yield signal by eliminating interference with heating current leakage and ground loops. The excellent operation of the cell is demonstrated with examples of CO and H₂ Fischer–Tropsch reactions on Co nanoparticles.     

Doping in poly(o-ethoxyaniline) nanostructured films studied with atomic force spectroscopy (AFS)

The study of intermolecular interactions at interfaces is essential for a number of applications, in addition to the understanding of mechanisms involved in sensing and biosensing with liquid samples. There are, however, only a few methods to probe such interfacial phenomena, one of which is the atomic force spectroscopy (AFS) where the force between an atomic force microscope tip and the sample surface is measured. In this study, we used AFS to estimate adhesion forces for a nanostructured film of poly(o-ethoxyaniline) (POEA) doped with various acids, in measurements performed in air. The adhesion force was lower for POEA doped with inorganic acids, such as HCl and H₂SO₄, than with organic acids, because the counterions were screened by the ethoxy groups. Significantly, the morphology of POEA both in the film and in solution depends on the doping acid. Using small-angle X-ray scattering (SAXS) we observed that POEA dissolved in a mixture of dimethyl acetamide exhibits a more extended coil-like conformation, with smaller radius of gyration, than for POEA in water, as in the latter POEA solubility is lower. In AFS measurements in a liquid cell, the force curves for a POEA layer displayed an attractive region for pH ≥ 5 due to van der Waals interactions, with no contribution from a double-layer since POEA was dedoped. In contrast, for pH ≤ 3, POEA was doped and the repulsive double-layer force dominated. With AFS one is therefore able to correlate molecular-level interactions with doping and morphology of semiconducting polymers.