Determination of order parameter of YMn0.5Fe0.5O3 epitaxial thin films by anomalous X-ray scattering technique

The crystal structure of an orthorhombic YMn_0.5Fe_0.5O₃ (010) (YMFO) epitaxial films on YAlO₃(010) substrate was studied using X-ray diffraction, X-ray absorption spectroscopy, and anomalous X-ray diffraction techniques. Due to the utmost similar scattering factors of Mn and Fe atoms, it is hard to distinguish them at specific sites of the unit cell from the variations in the diffraction peak intensity. Therefore, anomalous X-ray scattering was used to determine the order or disorder structure of YMFO films. To estimate the order parameter of the YMFO film, the incident X-ray energies have been scanned around the Mn K-edge and Fe K-edge, resulting in enhanced diffraction intensities of the forbidden YMFO (010) peak by 15–20 times, respectively. This in turn revealed that YMFO films have a partially ordered structure of about 40 ± 10% in the epitaxially grown thin film.     

Resonant soft X-ray scattering in polymer science

Resonant soft X-ray scattering (RSoXS) is an emerging, powerful technique to probe the nano-to-mesoscale structure of polymers and other molecules. It joins together small-angle X-ray scattering (a statistical nanoprobe) with X-ray spectroscopy that brings with it unique chemical and bond-orientation sensitivity. Through over a decade of discovery and development, RSoXS is moving from a niche technique applied to organic electronic thin films to a mature tool applicable to a plethora of polymeric and molecular systems, encompassing new modalities, analyses, and simulation methods. This development promises to deliver increasingly quantitative answers to challenging questions in polymer science as well as expand its usefulness to complementary fields. This review presents a full synopsis of the technique, including background on the theoretical underpinnings, measurement best practices, and examples of recent RSoXS applications and discoveries provided here to accelerate the transition to a broader range of soft matter and polymeric fields.     

Some aspects of lateral chain order in cellulosics from X-ray scattering

This paper gives an overview of our recent research activities on the lateral supramolecular order of a variety of native and man-made cellulosics considering respective results from the literature. Wide-angle X-ray scattering (WAXS) was the main investigation technique used. Lateral root mean squared lattice strains between 2 and 3% were determined for the materials investigated. Crystallite sizes obtained without considering lattice distortions usually do not deviate by much more than –10% from the real, i.e. fully corrected values. This means that it is sufficient to use the simple Scherrer equation for determining lateral crystallite sizes for most routine investigations of cellulosic materials. The possible superposition of WAXS peaks of the triclinic I and monoclinic I lattice types, however, has to be considered in crystallite size determinations for Valonia cellulose. It could be shown that neglecting this fact can lead to crystallite sizes being about 20% below the true ones. Lateral crystallite dimaensions for native celluloses vary between 4nm (dissolving pulps) and 10-15 nm (Valonia). Except for bacterial cellulose, the WAXS crystallite sizes are distinctly smaller than the microfibril dimensions obtained from electron microscopy. The man-made fibres investigated showed lateral crystallite dimensions between 3 and 5nm. The importance of lateral crystallite dimensions for the properties of man-made fibres and for the alkalization process of native cellulose id demonstrated.     

Rotor-synchronized two-dimensional 13C CP/MAS NMR studies of the orientational order of polymers. I. High-performance ultrahigh molecular weight polyethylene fibers

The orientational order of three morphological components, identified previously as two crystalline components, C₁ and C₂, and an amorphous component, A of four polyethylene fibers, including two gelspun ultrahigh molecular weight (PE-I and PE-II) and two meltspun moderate molecular weight (PE-D and PE) polyethylene fibers are further analyzed by rotor-synchronized two-dimensional ¹³C CP/MAS (ROSMAS) nuclear magnetic resonance (NMR) techniques. Our results indicate that the orientational order of these components differ substantially among themselves in a given fiber and among different fibers of the same component. Values of β_1/2, the polar angle at which the orientational distribution function (ODF) P 〈β〉 decays to half its maximum, are determined to be: 18° (C2 of PE-II), 21° (C2 of PE-I), 29° (C2 of PE-D), 31° (C1 of PE-I) and 50° (C2 of PE). No orientational sideband can be detected for component A, suggesting that the A component is due to the amorphous domain. The implication of this results and the technical limit of this technique are analyzed. © 1993 John Wiley & Sons, Inc.     

Order parameter studies from effective order geometry in 4O.Om and 7O.Om liquid crystalline compounds

The effective geometry parameter, α_g = n _o /n _e, is used to evaluate the orientational order parameter, S, in the case of N-(p-n-butyloxybenzylidene)-p-n-alkoxy anilines, 4O.Om and N-(p-n-heptyloxybenzylidene)-p-n-alkoxy anilines, 7O.Om compounds with m?=?3–7 and 9 in the former case and m?=?3, 5–7 and 9 in the later materials. The results obtained are compared with those calculated using the standard techniques of molecular polarisability and birefringence. The effective geometry parameter's influence on the deflection of light by the liquid crystal compounds is also studied. The variation of temperature gradient of the ordinary refractive index, dn _o /dT, and extraordinary refractive index, dn _e /dT, of the liquid crystals is also studied.     

Rotor-synchronized two-dimensional 13C CP/MAS NMR studies of the orientational order of polymers 2. Melt-extruded poly(ethylene terephthalate) fibers

Determination of the orientational order of morphological components in polyethylene terephthalate (PET) is sought through quantitative application of two-dimensional rotor synchronized magic angle spinning (ROSMAS) ¹³C NMR technique. Previous study in our laboratories had established a procedure for resolution of the carbonyl carbon (CA) and glycol ethylene carbon (GE) resonances into those corresponding to four morphological components.¹ Due to paucity of sidebands in the GE resonances, the focus has been on the CA resonances in this attempt to obtain orientation distributions. A set of PET fibers possessing a broad range of crystalline and orientational order has been used to infer the meaning of NMR-based orientation measurements vis-a-vis other techniques. A surprising finding of this study is the observation that the orientational orders of the broad component in the ¹³C CP/MAS spectrum and the narrow component are very similar in these fibers. ©1995 John Wiley & Sons, Inc.     

Multiple small-angle X-ray scattering analyses of the structure of gold nanorods with unique end caps

Small-angle X-ray scattering (SAXS) experiments were carried out on gold nanorods generated by a seed-mediated growth method. Previous transmission electron microscopy observations suggest that the main components of nanoparticles are rod-shaped nanoparticles, but they are contaminated by other different-shaped, large-volume particles. By performing profile fitting of theoretical and experimental scattering curves, we determined and then removed from the obtained SAXS profile, the contribution of the contaminating particles. From the revised SAXS profile, we calculated the distance distribution function by Fourier transform and precisely determined the structural parameters of the nanorods and the structure of the nanorod end caps.     

Molecular shape and orientational order. Effects in the energy of cavity formation in liquids

A recently proposed method for calculating the energy of cavity formation in liquids is presented in which the cavity formation process is described as work against the surface forces of the solvent, at the microscopic scale. The energy involved in the cavity formation process is, on the other hand, viewed as a strictly interaction potential energy and the reference cavity, which has the size and the shape of the space occupied by each molecule in the liquid, is considered as having short-range orientational order characteristic of the pure liquid. The method is successfully applied to binary alkane mixtures at infinite dilution whose components have different chemical structure (linear, cyclic and branched alkanes). The importance of the changes in the molecular order of the solute and the solvent occuring in the mixing process is emphasized.     

Viscosity reduction in polymer nanocomposites: Insights from dynamic neutron and X-ray scattering

The addition of nanoparticles to a polymer matrix can in certain cases induce a reduction in viscosity, with respect to the pure matrix, in the resulting composites. This counterintuitive phenomenon cannot be explained using the most common rheological models. For this reason, it has been chosen as a good example in this paper to demonstrate the value and methods of dynamic X-ray and neutron scattering techniques for the investigation of polymer nanocomposites. An overview of the main results on this topic is presented together with an introduction to the basic concepts relating to X-ray photon correlation spectroscopy, neutron backscattering, and neutron spin echo measurements.     

Study of orientational order in a nematic polysiloxane by utilizing the “guest–host” effect

A nematogenic side-chain polysiloxane is investigated by means of absorption and fluo-rescence spectroscopy.4-Dimethylamino-4′-nitrostilbene (DANS) is dissolved in the poly-meric matrix as a guest probe. The orientational order and the molecular distribution function have been determined from measurements of polarized absorption and fluorescence spectra. It has been found that fluorescence spectroscopy affords a method for determination of the phase transition temperatures of liquid–crystalline polymers. © 1993 John Wiley & Sons, Inc.     

Direct observation of scattering contributions in X-ray attenuation measurements, and evidence for Rayleigh scattering from copper samples rather than thermal-diffuse or Bragg–Laue scattering

High-precision attenuation measurements can now lead to a direct assessment of scattering models in the X-ray regime. This is true not just at high energies but even when scattering cross-sections typically lie below 0.1% of the photoelectric absorption cross-section. This allows model-independent results to be obtained in these attenuation experiments for the first time.     

Understanding liquid crystal order parameters deduced from different vibrations in polarised Raman spectroscopy

Polarised Raman Spectroscopy (PRS) has been used to measure order parameters in liquid crystalline materials for decades. However, it is well known that different values of the order parameters are deduced for the same material when different vibrational modes are used in the analysis. This is an undesirable discrepancy that has somewhat hindered the use of the technique. Here we use two Raman active bands namely the phenyl (1606 cm^?1) and cyano (2220 cm^?1) stretching modes in the nematic phase of 5CB (4-cyano-4?-pentylbiphenyl) as the example to explore the origin of such discrepancy. Two approaches are proposed in the data a nalysis taking either non-axial or non-cylindrical symmetric vibration into consideration. Together with a systematic discussion based on experimental data, we can conclude that whether or not the vibration satisfies the conditions associated with cylindrical symmetry is the correct physical explanation for the discrepancy in the order parameters.     

Development of nonuniform micropore structure of carbon adsorbents during activation: adsorption and small-angle X-ray scattering studies

The development of the micropore structure of activated carbons during activation was studied by small-angle X-ray scattering and adsorption methods. A new method for the processing of experimental data was used; this method makes it possible to obtain curves of the dimension distribution of micropores from the intensities of small-angle X-ray scattering and the adsorption isotherm. In the initial stage of activation, up to burnouts 0.3, the micropore structure is uniform, micropores with radius of gyration under 0.5–0.6 nm dominate. When activation is more prolonged ( = 0.3÷0.67), a bimodal system withR ₁ ^max 0.6 nm andR ₂ ^max 0.85÷1.0 nm forms, and the volume of large micropores (supermicropores) exceeds that of small ones considerably.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 231–235, February, 1994.     

Short-range order in some polymer melts from X-ray diffraction

Wide-angle X-ray diffraction measurements were performed on polymer melts of isotactic and syndiotactic polypropylene (IPP and SPP), poly(ethylenepropylene) (PEP), polystyrene (PS), polyisobutylene (PIB), and polyethylene (PE), to study the dependence of the short-range structure of polymer liquids on chain architecture. Total structure functions, which comprise intra- and intermolecular contributions, were derived from the scattering data. The trivial Fourier components of the intramolecular structure (C(SINGLE BOND)>C ≃ 1.54 Å and C(SINGLE BOND)C(SINGLE BOND)C ≃ 2.55 Å) were subtracted from the total structure functions. The remaining functions contain only those intramolecular contributions dependent on the chain's conformational degrees of freedom, plus the intramolecular contributions. The structural differences between the polymers in momentum space are discerned only when the trivial components are subtracted. This subtraction also reduces the effects of truncation errors on Fourier transformation to real space. The short-range structure of PIB appears very different compared to all the others, which correlates with anomalies in a number of physical properties for this polymer. © 1996 John Wiley & Sons, Inc.     

Small-angle X-ray scattering study on the microstructure evolution of zirconia nanoparticles during calcination

Zirconia nanoparticles have been synthesized from zirconium hydroxide precipitates followed by a supercritical CO₂ extraction. The microstructure evolution of these zirconia nanoparticles during the calcination at the moderate temperature has been investigated. Assisted by the analyses of TEM and XRD, small-angle X-ray scattering (SAXS) study offers possibilities to a comprehensive and quantitative characterization of the structural evolution on the nanometer scales. The as-synthesized zirconia sample exhibits a mass fractal structure constructed by the surface fractal particles. Such a structure can be preserved up to 300 °C. After calcination at 400 °C, considerable structural rearrangement occurs. In the interior of nanoparticles zirconia nanocrystallites emerge. It is the scattering from such zirconia nanoparticles that give rise to the broadened crossover in the ln[J(q)] vs. ln q plot and the scattering peak in the ln[q³J(q)] vs. q² plot. With a further increase in the calcination temperature, the power-law region at large-q in ln J(q) vs. ln q plot expands, and the peak in ln[q³J(q)] vs. q² plot shifts towards lower q values, indicating size increases in both the nanocrystallites and nanoparticles. Besides, the mass fractal structure constructed by zirconia nanoparticles can be largely preserved during the moderate temperature calcination.     

Conformational analysis of oriented non-crystalline polymers using wide angle X-ray scattering

A procedure is presented for obtaining conformational parameters from oriented but non-crystalline polymers. This is achieved by comparison of the experimental wide angle X-ray scattering with that calculated from models but in such a way that foreknowledge of the orientation distribution function is not required. X-ray scattering intensity values for glassy isotactic poly(methylmethacrylate) are analysed by these techniques. The method could be usefully applied to other oriented molecular systems such as liquid crystalline materials.     

Small-angle X-ray scattering studies of the open and closed conformations of aspartate aminotransferase

Summary Aspartate aminotransferase was investigated by X-ray small-angle scattering. A small difference was found between the open (active) and the closed (liganded) conformation of the enzyme. The results were compared with X-ray crystallography data.

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Untersuchungen zur Röntgenkleinwinkelstreuung der offenen und geschlossenen Konformation von Aspartat-Aminotransferase

Zusammenfassung Aspartat-Aminotransferase wurde mittels Röntgenkleinwinkelstreuung untersucht. Ein kleiner Unterschied zwischen der offenen (aktiven) und der geschlossenen (ligandierten) Konformation wurde gefunden. Die Ergebnisse wurden mit Röntgenkristallstrukturdaten verglichen.

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Abbreviations AspAT aspartate aminotransferase