Situ Small-angle X-ray Scattering Research Articles

Synthesis of 1 nm Pd Nanoparticles in a Microfluidic Reactor: Insights from in Situ X-ray Absorption Fine Structure Spectroscopy and Small-Angle X-ray Scattering

A novel microfluidic reactor for in situ small-angle X-ray scattering (SAXS) and X-ray absorption fine structure spectroscopy (XAFS) of Pd colloidal nanoparticles synthesis is reported. The microreactor allows time resolution ranging from milliseconds to several minutes with a residence time of over an hour. The synthesis of colloidal Pd nanoparticles is investigated in the presence of oleylamine and trioctylphosphine ligands. For both ligands, SAXS results show the synthesis proceeds through slow, continuous nucleation as evidenced by a continuous increase in the number of particles. Growth is autocatalytic and fast at the early times; then, despite the availability of a large percentage of unreacted Pd precursor, growth slows dramatically and the Pd nanoparticle diameter reaches a plateau while more nanoparticles continue to form. In situ XAFS reveals an increase in Pd–P coordination coinciding with the time of slowed growth. The combined SAXS and XAFS results strongly suggest that the capping ligands p...

Small Angle X-ray Scattering of Iron Oxide Nanoparticle Monolayers Formed on a Liquid Surface

In situ small-angle X-ray scattering (SAXS) is used to show that iron oxide nanoparticles (NPs) of a range of sizes form hexagonally ordered monolayers (MLs) on a diethylene glycol liquid surface, after drop-casting the NPs in hexane and subsequent hexane evaporation. The formation of the ordered NP ML is followed in real time by SAXS when using a heptane solvent. During drying, the NPs remain in the hexane or heptane layer, and an ordered structure is not formed then. After drying, the NPs are farther apart than expected from only van der Waals attraction between the NP cores and Brownian motion considerations, which suggests the importance of ligand attraction in binding the NPs.

(Invited) In Situ Small-Angle X-Ray Scattering for the Analysis of Electrochemical Degradation of Metal Oxide Supported Pt Nanoparticles

In current research on oxygen reduction reaction (ORR) catalysts for polymer electrolyte fuel cell (PEFC) cathodes, metal oxide supported Pt nanoparticles are considered to be one promising alternative to the standard carbon supported Pt, which offers the possibility of higher durability in the oxidizing environment at the PEFC cathode [1]. Detailed studies of the stability of Pt/metal oxide catalysts require the determination of the structure and surface area of the Pt nanoparticles during electrochemical durability testing. In situsmall-angle X-ray scattering (SAXS) offers the unique opportunity not only to monitor the evolution of the Pt nanoparticle size distribution in an electrochemical environment, but also to observe the evolution of the total Pt mass loading of the electrode at the same time. Furthermore, information about the dispersion/agglomeration of the Pt nanoparticles on the support surface can be inferred. Thus, the overall observed degradation of the electrochemically active surface area (ECSA) can be further analyzed in terms of different degradation phenomena like Pt loss due to dissolution, Pt nanoparticle growth due to electrochemical Ostwald ripening, and Pt nanoparticle migration and agglomeration. We have performed electrochemical in situ anomalous SAXS experiments, for the first time, on metal oxide supported Pt nanoparticles. The support consisted of a mixed iridium oxide-titanium oxide (IrO2-TiO2). The anomalous changes of the elemental scattering cross sections around the Pt LIII and the Ir LIII absorption edges were used to separate the Pt scattering contribution from the support scattering. This approach of anomalous SAXS was previously used for in situ studies of conventional carbon supported Pt [2,3]. Our results not only show that it is possible in this way to obtain a precise net Pt scattering signal even in the presence of a strongly scattering support material, but they also demonstrate clearly the existence of a previously neglected scattering interference effect due to the spatial correlations between Pt nanoparticles and support particles. This effect can become very strong for support materials containing high-Z elements like the IrO2-TiO2 support investigated in this study. However, we could also show that these particle-support interferences are non-negligible even for weakly scattering carbon supports. We developed a novel analytical tool to take the particle-support interferences into account in the data fitting procedure with high accuracy [4]. This approach highly improves the quantitative analytical power of SAXS studies on supported catalyst materials. We applied the novel method to the analysis of in situ SAXS data from Pt/IrO2-TiO2 to study the degradation properties of this ORR catalyst during harsh electrochemical potential cycling between 0.5 V and 1.5 V vs. RHE in 0.1 M HClO4. This protocol simulates the oxidative conditions during PEFC start/stop cycles [5]. The results not only reveal a Pt particle growth due to electrochemical Ostwald ripening and a concomitant Pt mass loss due to dissolution, but also indicate a possible influence of the X-ray beam on the catalyst degradation. Hence, on the one hand, the X-ray exposure time of the catalyst must be chosen long enough in order to achieve a good signal-to-noise ratio, but on the other hand, it must be short enough to prevent X-ray induced catalyst degradation. In summary, our findings pave the way to a detailed and quantitative in situ analysis of Pt nanoparticle degradation on various metal oxide support materials. Acknowledgments This work was supported by CCEM Switzerland and Umicore AG & Co KG within the project DuraCat. We acknowledge the Paul Scherrer Institut, Villigen, Switzerland, for provision of synchrotron radiation beamtime at the cSAXS beamline of the SLS.

Self-Assembly of a Designed Alternating Arginine/Phenylalanine Oligopeptide.

A model octapeptide peptide consisting of an alternating sequence of arginine (Arg) and phenylalanine (Phe) residues, namely, [Arg-Phe]4, was prepared, and its self-assembly in solution studied. The simple alternating [Arg-Phe]4 peptide sequence allows for unique insights into the aggregation process and the structure of the self-assembled motifs. Fluorescence and UV-vis assays were used to determine critical aggregation concentrations, corresponding to the formation of oligomeric species and β-sheet rich structures organized into both spheroidal aggregates and highly ordered fibrils. Electron and atomic force microscopy images show globular aggregates and long unbranched fibers with diameters ranging from ∼4 nm up to ∼40 nm. Infrared and circular dichroism spectroscopy show the formation of β-sheet structures. X-ray diffraction on oriented stalks show that the peptide fibers have an internal lamellar structure, with an orthorhombic unit cell with parameters a ∼ 27.6 Å, b ∼ 9.7 Å, and c ∼ 9.6 Å. In situ small-angle X-ray scattering (SAXS) shows the presence of low molecular weight oligomers in equilibrium with mature fibers which are likely made up from 5 or 6 intertwined protofilaments. Finally, weak gel solutions are probed under gentle shear, suggesting the ability of these arginine-rich fibers to form networks.

Property development for biaxial drawing of ethylene-tetrafluoroehtylene copolymer films and resultant fractural behavior analyzed by in situ X-ray measurements.

The property development of the ethylene-tetrafluoroethylene copolymer (ETFE) membrane induced by simultaneous biaxial drawing was investigated. Commonly, tensile strength can be increased by drawing; conversely, tear resistance decreases. In this study, the balance between tensile strength and tear resistance for the resultant ETFE membrane was optimized achieved by a combination of lamination of low molecular weight (LMW) and high molecular weight (HMW) layers and subsequent biaxial drawing. The structural factor determining tear resistance of these biaxially drawn membranes was determined based on in situ small-angle X-ray scattering (SAXS) measurement during tensile deformation simulating tearing tests. Lozenge shaped scattering, which indicated inclined lamellae, was observed during such tensile deformation of the resultant membranes. Remarkably, this inclined lamellar structure was observed for the pure LMW membrane; however, it also appeared at the interface between LMW and HMW layers within biaxially drawn membranes. For the membrane exhibiting the highest tearing strength, the fraction of such inclined lamella increased up to the critical strain corresponding to the actual sample breaking. These results confirm that the inclined lamellar structure absorbed strain during membrane tearing.

Gelation of a solution of poly(3-hexylthiophene) greatly retards its crystallization rate in the subsequently cast film.

We compared the crystallization rate of poly(3-hexylthiophene) (P3HT) in the film cast from the gel (called "gel-cast film") with that in the film cast from the liquid solution (called "solution-cast film") to understand the effect of solution structure on the structural development in the subsequently cast film of conjugated polymer. P3HT was found to form a homogeneous liquid solution with xylene at elevated temperature. When the freshly prepared semidilute solution was allowed to age at room temperature, the solution transformed into a gel in which a significant amount of nanowhiskers formed. The nanowhiskers in the gel were effectively transferred to the corresponding cast film, while the film cast from the freshly prepared solution only contained a small amount of such a morphological entity. The in situ small-angle X-ray scattering (SAXS) measurement and thermal analysis revealed that both the cold and melt crystallization of P3HT in the gel-cast film were much slower than those in the solution-cast counterpart. The retardation of crystallization rate in the gel-cast film was attributed to the abundance of the nanowhiskers. In this case, the crystallization of P3HT occurred predominantly within the individual nanowhiskers and the mesh regions in the networks of the whiskers, where their limited sizes in at least one dimension imposed a strong spatial constraint to the crystal growth and chain motion for crystallization.

In situ SAXS study of dibromomethane adsorption on MCM-41

In situ small-angle X-ray scattering (SAXS) measurements, with the aid of a specially-designed cell, have been carried during CH2Br2 adsorption on MCM-41. Ordered mesoporous silicas consist of a 2D hexagonal array of cylindrical mesopores of uniform size. As a result, they exhibit Bragg peaks because of the regular packing of the cylindrical pores. Dibromomethane was selected as a contrast-matching fluid because it has almost the same electron density as silica. The SAXS patterns provide information about both the structural properties of MCM-41 and the adsorption mechanism. The power law observed in the low-Q regime can be ascribed to intergrain interfacial scattering. The intensity decrease and the elimination of the Bragg peaks for the saturated sample suggested that an almost perfect contrast matching was achieved. Finally, information about the growing thickness of the adsorbed film was obtained by analyzing the integrated intensities of the diffraction peaks with a structural model consisting of infinitely long concentric cylindrical shells with four levels of electron density.

Self-assembled CdSe/CdS nanorod sheets studied in the bulk suspension by magnetic alignment.

We studied spontaneously self-assembled aggregates in a suspension of CdSe/CdS core/shell nanorods (NRs). The influence of the length and concentration of the NRs and the suspension temperature on the size of the aggregates was investigated using in situ small-angle X-ray scattering (SAXS) and linear dichroism (LD) measurements under high magnetic fields (up to 30 T). The SAXS patterns reveal the existence of crystalline 2-dimensional sheets of ordered NRs with an unusually large distance between the rods. The LD measurements show that the size of the sheets depends on the free-energy driving force for NR self-assembly. More precisely, the sheets are larger if the attraction between NRs is stronger, if the temperature is lower, or if the NR concentration is higher. We show that the formation of large NR sheets is a slow process that can take days. Our in situ results of the structures that spontaneously form in the bulk suspension could further our understanding of NR self-assembly into mono- or multilayer superlattices that occurs at the suspension/air interface upon evaporation of the solvent.

Lamellae break induced formation of shish-kebab during hot stretching of ultra-high molecular weight polyethylene precursor fibers investigated by in situ small angle X-ray scattering

The extracted low-oriented ultra-high molecular weight polyethylene precursor fibers were stretched at the temperature of 80 °C. In situ small-angle X-ray scattering (SAXS) measurement using synchrotron radiation was applied to study the microstructure evolutions of fibers including the deformation and break of lamellae, the diminishing of microvoids, and the formation of shish-kebab. It was found that hot stretching could induce different kinds of SAXS patterns: two-point pattern indicating the stacking lamellae, X-shaped pattern indicating the tilted state of lamellae, the changing of streak pattern indicating the evolution of microvoids and shish structures respectively. During later stage of stretching, the shish structures along the fiber axis became remarkable to develop the final shish-kebab structures accompanied by the break-reorganization of original lamellae. The results also reveal the close relationship between macroscopic deformation and microstructural evolution that the macroscopic external stress loaded on internal microstructures can effectively promote the transformation from chain-folded lamellae to chain-extended crystals.

Fracture resistance of human cortical bone across multiple length-scales at physiological strain rates

While most fracture-mechanics investigations on bone have been performed at low strain rates, physiological fractures invariably occur at higher loading rates. Here, at strain rates from 10−5 to 10−1 s−1, we investigate deformation and fracture in bone at small length-scales using in situ small-angle x-ray scattering (SAXS) to study deformation in the mineralized collagen fibrils and at the microstructural level via fracture-mechanics experiments to study toughening mechanisms generating toughness through crack-tip shielding. Our results show diminished bone toughness at increasing strain rates as cracks penetrate through the osteons at higher strain rates instead of deflecting at the cement lines, which is a prime toughening mechanism in bone at low strain rates. The absence of crack deflection mechanisms at higher strain rates is consistent with lower intrinsic bone matrix toughness. In the SAXS experiments, higher fibrillar strains at higher strain rates suggest less inelastic deformation and thus support a lower intrinsic toughness. The increased incidence of fracture induced by high strain rates can be associated with a loss in toughness in the matrix caused by a strain rate induced stiffening of the fibril ductility, i.e., a “locking-up” of the viscous sliding and sacrificial bonding mechanisms, which are the origin of inelastic deformation (and toughness) in bone at small length-scales.

Ureasil-Poly(ethylene oxide) Hybrid Matrix for Selective Adsorption and Separation of Dyes from Water

Herein, we present a cross-linked ureasil-polyether-siloxane hybrid (labeled PEO500) that can function as a stimuli-sensitive material; it swells or shrinks in response to changes in the environmental conditions and it can also, effectively and selectively, remove dyes from water solution. We also developed a methodology to separate a mixture of cationic and anionic dyes present in water. Addition of PEO500 to an aqueous solution of the anionic orange II (OII) or the ponceau S (PS) dye rendered the solution colorless, but an aqueous solution of cationic methylene blue (MB) remained unchanged after 2 h of contact with the insoluble matrix. In situ small-angle X-ray scattering (SAXS) showed that the distance of siloxane nanodomains are strongly affected by the swelling or shriking. By in situ UV-vis adsorption experiments, we found that the kinetics of OII and PS removal followed a pseudo-first-order rate equation. We accomplished B3LYP calculations, to establish which sites on the matrix interacted with the dyes and to investigate the nature of the matrix-dye chemical bonds. On the basis of the experimental and theoretical investigations, we proposed some mechanisms to explain how PEO500 adsorbs anionic dyes efficiently. This "smart" matrix is potentially applicable as an efficient, fast, selective, and convenient device in water treatment and stimuli-sensitive response materials.

Quantitative description of the T1 formation kinetics in an Al–Cu–Li alloy using differential scanning calorimetry, small-angle X-ray scattering and transmission electron microscopy

The object of the present study is to design a methodology to follow the kinetics of T1 precipitation, in an AA2198 alloy, in terms of precipitate size, morphology (thickness, diameter) and volume fraction, during a two-temperature isothermal heat treatment. We used in situ small-angle X-ray scattering (SAXS) as a way to measure the evolution of the T1 mean thickness and diameter during the heat treatment. Transmission electron microscopy (TEM) was then performed in order to calibrate these evolutions. Furthermore, we demonstrate that the volume fraction evolution can be described successfully using a simple analysis of the differential scanning calorimetry (DSC) thermograms. The latter was calibrated by selected observations in high angular annular dark field scanning transmission electron microscopy (HAADF-STEM). Microstructure evolution during DSC heating ramps was analysed using in situ SAXS: the T1 phase transformation is found to consist in a two-step thickening process explained by two consecutive diffusion stages. The enthalpy of formation of the T1 phase is deduced from the DSC measurements.

Extension-Induced Crystallization of Poly(ethylene oxide) Bidisperse Blends: An Entanglement Network Perspective

The role of long chains in extension flow-induced crystallization was studied with a combination of extension rheological and in situ small-angle X-ray scattering (SAXS) measurements at 52 °C. To elucidate the effects of long chains, bidisperse blends of poly(ethylene oxide) (PEO) with the long-chain concentration above the overlap concentration were prepared, constructing long-chain entanglement network in short-chain matrix. Rheological data of step extension on PEO melt are divided into two regions with fracture strain of pure short-chain sample as a boundary. Distinctly different features of crystallization kinetics and crystal morphologies are observed in these two regions, exactly corresponding to rheological behavior. A new mechanism based on entanglement network perspective is proposed, in which the second entanglement network constructed by long chains has three effects: (i) helping flow to change the free energy of polymer melt more effectively; (ii) ensuring the specific work can impose on the ...

Counterion Distribution Surrounding Spherical Nucleic Acid–Au Nanoparticle Conjugates Probed by Small-Angle X-ray Scattering

The radial distribution of monovalent cations surrounding spherical nucleic acid-Au nanoparticle conjugates (SNA-AuNPs) is determined by in situ small-angle x-ray scattering (SAXS) and classical density functional theory (DFT) calculations. Small differences in SAXS intensity profiles from SNA-AuNPs dispersed in a series of solutions containing different monovalent ions (Na(+), K(+), Rb(+), or Cs(+)) are measured. Using the "heavy ion replacement" SAXS (HIRSAXS) approach, we extract the cation-distribution-dependent contribution to the SAXS intensity and show that it agrees with DFT predictions. The experiment-theory comparisons reveal the radial distribution of cations as well as the conformation of the DNA in the SNA shell. The analysis shows an enhancement to the average cation concentration in the SNA shell that can be up to 15-fold, depending on the bulk solution ionic concentration. The study demonstrates the feasibility of HIRSAXS in probing the distribution of monovalent cations surrounding nanoparticles with an electron dense core (e.g., metals).

Polymer crystallization studies under processing-relevant conditions at the SAXS/WAXS DUBBLE beamline at the ESRF

Recent developments on the experimental infrastructure and the acquisition of new detectors on the Dutch–Belgian beamline BM26B at the ESRF offer novel and promising possibilities for synchrotron X-ray experiments in the field of polymer crystallization under processing-relevant conditions. In this contribution, some of the most recent experiments mimicking conditions similar to those relevant for the plastics processing industry are discussed. Simultaneous thermal analysis and wide-angle X-ray scattering (WAXS) experiments, at the millisecond time-frame level, on β-nucleated isotactic polypropylene (i-PP) samples subjected to ballistic cooling up to 230 K s−1, show that the efficiency of the nucleating agent can be suppressed when quenched cooling rates higher than 130 K s−1are used.In situWAXS experiments using small-scale industrial equipment during a real film blowing process reveal the dependence of the onset of crystallinity (the so-called freeze line) and the crystal orientation as a function of different take-up and blow-up ratios.In situsmall-angle X-ray scattering (SAXS) experiments during high-flow fields reveal the formation of shish and kebab structures in i-PP as a function of the imposed stress. Quantitative analysis of i-PP flow-induced structures is presented. The beamline specifications required to obtain high quality and industrially relevant results are also briefly reported.

Direct Observation of Plugs and Intrawall Pores in SBA-15 Using Low Voltage High Resolution Scanning Electron Microscopy and the Influence of Solvent Properties on Plug-Formation

Through the use of low voltage high resolution scanning electron microscopy (LV-HRSEM) we have studied the fine details of the intricate pore structure of SBA-15. Intrawall pores and deviations from the ideal and uniform cylindrical pores are clearly observed, and we report for the first time the direct observation of “plugs” in the pores. N2-sorption measurements confirm their existence. LV-HRSEM provides an opportunity to quantify the frequency of occurrence of plugs within the pore structure. The rate of mesophase formation, followed with in situ small angle X-ray scattering (SAXS) under different solvent conditions, is shown to have a significant influence on the development of plugs and how frequently they occur. We suggest a mechanism explaining the existence of the plugs, providing means for a better understanding and control over material properties.

Self-Assembly Mechanism of Folate-Templated Mesoporous Silica

A method to form ordered mesoporous silica based on the use of folate supramolecular templates has been developed. Evidence based on in situ small-angle X-ray scattering (SAXS), electron microscopy, infrared spectroscopy, and in situ conductivity measurements are used to investigate the organic-inorganic interactions and synthesis mechanism. The behavior of folate molecules in solution differs distinctively from that of surfactants commonly used for the preparation of ordered mesoporous silica phases, notably with the absence of a critical micellar concentration. In situ SAXS studies reveal fluctuations in X-ray scattering intensities consistent with the condensation of the silica precursor surrounding the folate template and the growth of the silica mesostructure in the initial stages. High-angle X-ray diffraction shows that the folate template is well-ordered within the pores even after a few minutes of synthesis. Direct structural data for the self-assembly of folates into chiral tetramers within the pores of mesoporous silica provide evidence for the in register stacking of folate tetramers, resulting in a chiral surface of rotated tetramers, with a rotation angle of 30°. Additionally, the self-assembled folates within pores were capable of adsorbing a considerable amount of CO2 gas through the cavity space of the tetramers. The study demonstrates the validity of using a naturally occurring template to produce relevant and functional mesoporous materials.

How hexagonal mesoporous silica evolves in water on short and long term: Role of pore size and silica wall porosity

In this study, we have determined the evolution of the morphology and the structure of mesoporous silica MCM41 and SBA15 in saturation condition during short and long term alteration by water at 60°C. These materials were characterized using in situ/ex situ Small Angle X-ray Scattering (SAXS), and ex-situ by nitrogen adsorption–desorption and 29Si Nuclear Magnetic Resonance (NMR). The results have shown that MCM41 lost its hexagonal order of pores. This phenomenon has been attributed to a change of the pore shape probably due to the dissolution of silica wall and to the recondensation of hydrolysed silica on the pore surface leading also to a partial pore clogging at high alteration progress. In the case of SBA15, as soon as the porous silica is in contact with water, an altered silica layer is formed at the pore surface and dissolved at a rate of 120nmyear−1 leading to a pore size increase. When an equilibrium between dissolution and recondensation of the silica is reached, the silica dissolution rate strongly decreases (7nmyear−1) and the altered layer growth follows a diffusive process with a diffusion coefficient of D=1.4×10−24m2s−1. The differences of evolution between the two silica are explained by their different pore diameter and the presence of microporosity in the case of SBA15.

Self-Assembly of Condensable “Bola-Amphiphiles” in Water/Tetraethoxysilane Mixtures for the Elaboration of Mesostructured Hybrid Materials

The self-assembly of condensable amphiphile molecules in water is an attractive approach for the synthesis of mesostructured hybrid materials. In this article, we focus on aminoundecyltriethoxysilane (AUT), a condensable "bola-amphiphile", i.e., an amphiphilic molecule possessing two polar heads on both sides of an aliphatic chain. In the present case, one side is a condensable triethoxysilane, and the other side is an amino group. We report on the self-assembly of AUT in mixtures of water and tetraethoxysilane (TEOS). In situ small-angle X-ray scattering (SAXS) measurements allowed us to follow the evolution of the structure from the liquid state up to the solid material formed upon catalytic polycondensation. Depending on the medium composition, hexagonal or lamellar structures can be observed in the final material. These observations allowed us to propose a model for the self-assembly of AUT in water/TEOS mixtures that we were able to validate by simulations of the SAXS profiles. By taking advantage of the modularity of such a system, it proves possible to prepare in a simple way various structured hybrid materials possessing a high number of available organic functions without using sacrificial surfactant molecules.

In Situ Monitoring of the Reaction‐Induced Self‐Assembly of Phenolic Resin Templated by Diblock Copolymers

In this study, in situ small‐angle X‐ray scattering (SAXS), in situ Fourier transform infrared (FTIR) spectroscopy, and transmission electron microscopy (TEM) are used to monitor the formation of ordered mesophases in cured mixtures of phenolic resin and the diblock copolymer poly(ethylene oxide‐block‐ε‐caprolactone) (PEO‐b‐PCL). SAXS and TEM analyses reveal that the mesophase of the phenolic/PEO‐b‐PCL mixture transforms sequentially from disordered to short‐range‐ordered to hexagonal‐cylindrical to gyroidal during the curing process when using hexamethylenetetramine (HMTA) as a cross‐linking agent, indicating that a mechanism involving reaction‐induced microphase separation controls the self‐assembly of the phenolic resin. In situ SAXS is also used to observe the fabrication of mesoporous phenolic resins during subsequent calcination processes. image