Progress of diffraction enhanced imaging at the Beijing Synchrotron Radiation Facility

A simple framework that allows a new general diffraction enhanced imaging (DEI) equation to be derived is presented. This latter equation may explain all open problems associated with the equation introduced by Chapman and those not explained by the first DEI equation, such as the noise background due to the small-angle scattering reflected by the analyzer. Combing the DEI equation with computed tomography (CT) theory, we propose a new DEI–CT formula that explains qualitatively the contour contrast caused by extinction of the refraction. Two formulae with a new method to extract the refraction angle are also introduced. Within this new theoretical framework the three components of the gradient of the refractive index can be reconstructed.     

Lamellar morphology and equilibrium melting temperature of syndiotactic polystyrene in β‐crystalline form

Lamellar morphology and thickness of syndiotactic polystyrene (sPS) samples melt‐crystallized at various temperatures were probed using transmission electron microscopy (TEM) and small‐angle X‐ray scattering (SAXS). In addition, the melting temperature and enthalpy of the crystallized samples were characterized with differential scanning calorimetry. Under appropriate thermal treatments, all the samples investigated in this study were crystallized into β′ crystal modification, as revealed by wide‐angle X‐ray diffraction. From the SAXS intensity profiles, a scattering peak (or shoulder) associated with lamellar features as well as the presence of anomalous scattering at the zero‐scattering vector were evidently observed. The peculiar zero‐angle scattering was successfully described by the Debye–Bueche model, and subtraction of its contribution from the raw intensity profiles was carried out to deduce the intensity profile merely associated with the lamellar feature. The lamellar thickness obtained from Lorentz‐corrected intensity profiles in this manner agrees with that measured from the TEM images, provided that the two‐phase model is applied. On the basis of the Gibbs–Thomson equation, the modest estimations of equilibrium melting temperature and the surface free energy of the fold lamellar surface are 292.7 ± 2.7 °C and 20.2 ± 2.6 erg/cm², respectively, when lamellar thicknesses measured by TEM are applied. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1626–1636, 2002     

In situ observation of homogeneous nucleation of nanosized zeolite A

The formation of zeolite A (LTA) in the presence of tetramethylammonium cations is studied using in situ small angle and wide angle X-ray scattering (SAXS/WAXS) techniques. The SAXS measurements show the formation of homogeneous precursors 10 nm in size prior to the crystallization of LTA which were consumed during the crystallization. The crystal size is estimated by fitting the SAXS patterns with an equation for a cubic particle, and it is revealed that the final crystal size of the LTA depends on the synthesis temperature. However, although such temperature dependence is noted for the final crystal size, the initial precursor particles size appears to be closely similar (ca. 10 nm) irrespective of the synthesis temperature.     

Formation of the background component of the analytical signal in the long-wavelength region of X-ray fluorescence spectrum

Components of X-ray background in the long-wavelength spectral region of a crystal diffraction X-ray fluorescence spectrometer were calculated. The calculations took into account the bremsstrahlung radiation of free electrons, diffuse scattering and fluorescence of the crystal analyzer, and high-order reflections of the scattered radiation of the fluorescent sample by the crystal analyzer. The results of calculations were compared with the intensities of background samples measured in the region of the NaK _α fluorescence line on an SRM-25 wave X-ray spectrometer. The experimental background intensities (response function) well correlate with those found by the regression equation with calculated factors. The importance of particular processes in the formation of X-ray background was assessed.     

Calculated absorption and scattering properties of gold nanoparticles of different size, shape, and composition: applications in biological imaging and biomedicine

The selection of nanoparticles for achieving efficient contrast for biological and cell imaging applications, as well as for photothermal therapeutic applications, is based on the optical properties of the nanoparticles. We use Mie theory and discrete dipole approximation method to calculate absorption and scattering efficiencies and optical resonance wavelengths for three commonly used classes of nanoparticles: gold nanospheres, silica-gold nanoshells, and gold nanorods. The calculated spectra clearly reflect the well-known dependence of nanoparticle optical properties viz. the resonance wavelength, the extinction cross-section, and the ratio of scattering to absorption, on the nanoparticle dimensions. A systematic quantitative study of the various trends is presented. By increasing the size of gold nanospheres from 20 to 80 nm, the magnitude of extinction as well as the relative contribution of scattering to the extinction rapidly increases. Gold nanospheres in the size range commonly employed ( approximately 40 nm) show an absorption cross-section 5 orders higher than conventional absorbing dyes, while the magnitude of light scattering by 80-nm gold nanospheres is 5 orders higher than the light emission from strongly fluorescing dyes. The variation in the plasmon wavelength maximum of nanospheres, i.e., from approximately 520 to 550 nm, is however too limited to be useful for in vivo applications. Gold nanoshells are found to have optical cross-sections comparable to and even higher than the nanospheres. Additionally, their optical resonances lie favorably in the near-infrared region. The resonance wavelength can be rapidly increased by either increasing the total nanoshell size or increasing the ratio of the core-to-shell radius. The total extinction of nanoshells shows a linear dependence on their total size, however, it is independent of the core/shell radius ratio. The relative scattering contribution to the extinction can be rapidly increased by increasing the nanoshell size or decreasing the ratio of the core/shell radius. Gold nanorods show optical cross-sections comparable to nanospheres and nanoshells, however, at much smaller effective size. Their optical resonance can be linearly tuned across the near-infrared region by changing either the effective size or the aspect ratio of the nanorods. The total extinction as well as the relative scattering contribution increases rapidly with the effective size, however, they are independent of the aspect ratio. To compare the effectiveness of nanoparticles of different sizes for real biomedical applications, size-normalized optical cross-sections or per micron coefficients are calculated. Gold nanorods show per micron absorption and scattering coefficients that are an order of magnitude higher than those for nanoshells and nanospheres. While nanorods with a higher aspect ratio along with a smaller effective radius are the best photoabsorbing nanoparticles, the highest scattering contrast for imaging applications is obtained from nanorods of high aspect ratio with a larger effective radius.     

SIMULTANEOUS SAXS／WAXS／DSC STUDIES ON MICROSTRUCTURE OF CONVENTIONAL AND METALLOCENE-BASED ETHYLENE-BUTENE COPOLYMERS

The fractions of one metallocene-based (mPE) and one conventional (znPE) ethylene-butene copolymer eluted at 80-82℃ from temperature rising elution fractionation were selected for DSC and time-resolved small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS) characterization. The DSC and WAXS results show that two crystal structures exist in both mPE and znPE: structure A with higher melting temperature and structure B with lower melting temperature. It was found that original znPE (s-znPE) contains more highly ordered structure A than original mPE (s-mPE) in spite of the higher comonomer content of znPE. Another structure C is also identified because of higher crystallinity measured by WAXS than by DSC and is attributed to the interfacial region. The SAXS data were analyzed with correlation function and two maxima were observed in s-mPE and s-znPE, in agreement with the conclusion of two crystal populations drawn from DSC and WAXS results. These two crystal populatiorts have close long periods in s-mPE, but very different long periods in s-znPE. In contrast, freshly crystallized mPE and znPE (f-mPE and f-znPE) contain only a single crystal population with a broader distribution of long period     

Small angle X-ray scattering pole figures of semicrystalline polymers obtained by synchrotron radiation

A goniometer for measuring small angle X-ray scattering pole figures by using synchrotron radiation has been constructed. In order to obtain the scattering in a large range of scattering angles, position-sensitive detectors (Gabriel counter and vidicon system) are applied. The integrated intensity as well as the position and the half width of the maximum are determined as functions of the angle between the incident beam and the normal to the film surface of the sample. The time necessary to determine a pole figure was approximately 3 hours. Samples of poly(ethylene terephthalate) were drawn under different conditions: uniaxially and biaxially at 92°C under homogeneous deformation, and uniaxially at 40°C by necking. The influence of the drawing conditions on the orientation of the crystal lamellae was determined. The results of the small angle scattering are compared with pole figures obtained by wide angle scattering. In addition some results with polypropylene were obtained. The small angle X-ray scattering is strongly affected by the limited size of the crystals and by the incomplete regular arrangement of the crystals. This gives rise to difficulties in the interpretation of the results. The problem will be discussed.     

Effects of elastic scattering and analyzer‐acceptance angle on the analysis of angle‐resolved X‐ray photoelectron spectroscopy data

We have made calculations of N 1s, O 1s, Si(oxide) 2p, Hf 4f, and Si(substrate) 2p photoelectron intensities at selected emission angles for films of SiO_1.6N_0.4 and HfO_1.9N_0.1 of various thicknesses on silicon. These calculations were made with the National Institute of Standards and Technology (NIST) Database for Simulation of Electron Spectra for Surface Analysis (SESSA) to investigate effects of elastic scattering and analyzer‐acceptance angle that could be relevant in the analysis of angle‐resolved X‐ray photoelectron spectroscopy (ARXPS) experiments. The simulations were made for an XPS configuration with a fixed angle between the X‐ray source (i.e. for the sample‐tilting mode of ARXPS) and with Al and Cu Kα X‐ray sources. The no‐loss intensities changed appreciably as elastic scattering was switched ‘on’ and ‘off’, but changing the analyzer‐acceptance angle had a smaller effect. Ratios of intensities for each line from the overlayer film for the least realistic model condition (elastic scattering switched ‘off’, small analyzer‐acceptance angle) to those from the most realistic model condition (elastic scattering switched ‘on’, finite analyzer‐acceptance angle) changed relatively slowly with emission angle, but the corresponding intensity ratio for the Si(substrate) 2p line changed appreciably with emission angle. The latter changes, in particular, indicate that neglect of elastic‐scattering effects can lead to erroneous results in the analysis of measured ARXPS data. The elastic‐scattering effects were larger in HfO_1.9N_0.1 than in SiO_1.6N_0.4 (due to the larger average atomic number in the former compound) and were larger with the Al Kα X‐ray source than with the Cu Kα source because of the larger cross sections for elastic scattering at the lower photoelectron energies. Copyright © 2010 John Wiley & Sons, Ltd.     

X-射线衍射法测定尼龙1010结晶度

根据X-射线散射强度理论,使用图解多重峰方法对尼龙1010三个结晶峰及非晶峰的衍射强度进行校正,首次导出了尼龙1010结晶度计算公式,所得结果与密度及量热测定结果具有很好可比性。     

Strain‐induced compression of smectic layers in free‐standing liquid crystalline elastomer films

The deformation of oriented smectic liquid crystal elastomer films with smectic layers parallel to the film surface was studied using optical reflectometry and small angle X‐ray diffraction. Reflectometry data show that in the chosen material, in‐plane strain causes a change in the optical thickness of the free‐standing films. Small angle X‐ray scattering was used to explore the molecular origin of this effect. The X‐ray scattering data confirm that the change in optical thickness originates from the compression of the individual smectic layers. The measured Poisson ratio in the smectic A and C* phases is close to ½, in contrast to the smectic elastomers investigated earlier by Nishikawa et. al. [Macromol. Chem. Phys. 200, 312 (1999)]. In this unique material, the molecular lattice dimensions can be reversibly controlled by macroscopic stretching of the oriented samples.     

Quantitative impact of small angle forward scatter on whole blood oximetry using a Beer-Lambert absorbance model

It is well known that red blood cell scattering has an impact on whole blood oximetry as well as in vivo retinal oxygen saturation measurements. The goal of this study was to quantify the impact of small angle forward scatter on whole blood oximetry for scattering angles found in retinal oximetry light paths. Transmittance spectra of whole blood were measured in two different experimental setups: one that included small angle scatter in the transmitted signal and one that measured the transmitted signal only, at absorbance path lengths of 25, 50, 100, 250 and 500 μm. Oxygen saturation was determined by multiple linear regression in the 520-600 nm wavelength range and compared between path lengths and experimental setups. Mean calculated oxygen saturation differences between setups were greater than 10% at every absorbance path length. The deviations to the Beer-Lambert absorbance model had different spectral dependences between experimental setups, with the highest deviations found in the 520-540 nm range when scatter was added to the transmitted signal. These results are consistent with other models of forward scatter that predict different spectral dependences of the red blood cell scattering cross-section and haemoglobin extinction coefficients in this wavelength range.     

Synchrotron SAXS and WAXS Studies on Changes in Structural and Thermal Properties of Poly[(R)‐3‐hydroxybutyrate] Single Crystals during Heating

Summary: The annealing and melting behavior of poly[(R)‐3‐hydroxybutyrate] (P(3HB)) single crystals were followed in real time by synchrotron small‐ (SAXS) and wide‐angle X‐ray scattering (WAXS) measurements. The real‐time SAXS measurements revealed that the P(3HB) single crystal exhibits a discontinuous increase of lamellar thickness during heating. The structural changes as observed by SAXS and WAXS were in response to the thermal properties of single crystals characterized by differential scanning calorimetry.

A series of two‐dimensional small‐angle X‐ray scattering patterns of P(3HB) single crystal mats during the lamellar thickening process.     

黄原胶溶致液晶行为的研究

以小角激光光散射法、偏光显微镜法及旋转粘度计法研究了黄原胶水溶液在不同浓度和温度下的光学性质。结构区域及粘性行为。发现当溶液浓度达到3％(临界浓度值)时,呈现胆甾型液晶特征,液晶的形成对温度有显著的依赖性。     

Molecular characterization of a hyperbranched polyester. II. Small‐angle neutron scattering

A series of fractions of a hyperbranched polyester in deutero tetrahydrofuran solution were investigated by small‐angle neutron scattering. Concentrations of polymer from 2 to 5% w/v were used, and the molecular parameters were obtained from Zimm plots of the data. Second virial coefficients were positive, and these values were confirmed by dilute‐solution light scattering on a small number of fractions with deutero tetrahydrofuran as a solvent. The small‐angle neutron scattering data exhibited the general features predicted for the particle scattering functions of nonrandomly branched polymers, but an exact fit of the theoretical equation to the data could not be obtained for all fractions of the hyperbranched polymer, particularly those of high molecular weight. Excluded volume effects were cited as a possible cause for this disagreement. A fractal dimension of ～2.5 was obtained from the scattering vector dependence of the differential scattering cross section of the polymer in deutero tetrahydrofuran solution, which agreed with the scaling exponent for the dependence of the radius of gyration on weight‐average molecular weight. Hydrogenous tetrahydrofuran solutions of the hyperbranched polymer exhibited negative second virial coefficients that were attributed to isotopic influences on the thermodynamic properties of the polymer–solvent combination. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1352–1361, 2003     

Contrast ratio of twisted nematic liquid crystal cells and its improvement

The light leakage of twisted nematic (TN) liquid crystal displays is investigated. While the TN mode has a robust structure in regard to light scattering, due to thermal fluctuations of the liquid crystals and light leakage from imperfect rubbing defects, it maintains significant residual retardation of the liquid crystal layer in the black state. The residual retardation is induced by the azimuthally twisted liquid crystal alignment near substrate surfaces and causes major light leakage in the black state. We investigated several methods to compensate for the residual retardation, and the methods include the adjustment of the helical power of the liquid crystal material, the increase of driving voltage, the control of rubbing direction and a newly designed compensation film with a small angle twist. Though all these methods improve the contrast ratio by about 30%, each method has its own weaknesses and limitations. The development of a new compensation film would provide a good chance for future TN applications.     

PNIPAM-co-polystyrene core-shell microgels: structure, swelling behavior, and crystallization

The present contribution presents the single-step preparation and characterization of poly(N-isopropyl acrylamide)-co-polystyrene core-shell microgels with varying polystyrene content. The swelling behavior of the particles is investigated using dynamic light scattering and differs significantly from the swelling behavior of poly(N-isopropyl acrylamide) homopolymer particles. The lower critical solution temperature is found to be shifted to lower temperatures upon increasing the polystyrene content of the particles. The core-shell structure of the particles is revealed by means of small angle neutron scattering (SANS) using the method of contrast variation. Additionally, the formation of mesoscopic crystals of these particles is investigated by means of scanning electron microscopy and also by SANS. The particles seem to have preferable properties with respect to crystallization compared to homopolymer microgels.     

Crystallization behavior of isotactic propylene‐1‐hexene random copolymer revealed by time‐resolved SAXS/WAXD techniques

The crystallization behavior of isotactic propylene‐1‐hexene (PH) random copolymer having 5.7% mole fraction of hexene content was investigated using simultaneous time‐resolved small‐angle X‐ray scattering (SAXS) and wide‐angle X‐ray diffraction (WAXD) techniques. For this copolymer, the hexene component cannot be incorporated into the unit cell structure of isotactic polypropylene (iPP). Only α‐phase crystal form of iPP was observed when samples were melt crystallized at temperatures of 40 °C, 60 °C, 80 °C, and 100 °C. Comprehensive analysis of SAXS and WAXD profiles indicated that the crystalline morphology is correlated with crystallization temperature. At high temperatures (e.g., 100 °C) the dominant morphology is the lamellar structure; while at low temperatures (e.g., 40 °C) only highly disordered small crystal blocks can be formed. These morphologies are kinetically controlled. Under a small degree of supercooling (the corresponding iPP crystallization rate is slow), a segmental segregation between iPP and hexene components probably takes place, leading to the formation of iPP lamellar crystals with a higher degree of order. In contrast, under a large degree of supercooling (the corresponding iPP crystallization rate is fast), defective small crystal blocks are favored due to the large thermodynamic driving force and low chain mobility. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 26–32, 2010     

Dependence of the enhanced optical scattering efficiency relative to that of absorption for gold metal nanorods on aspect ratio, size, end-cap shape, and medium refractive index

The current intense interest in the properties of plasmonic nanostructures for their applications in chemical and biochemical sensors, medical diagnostics and therapeutics, and biological imaging is fundamentally based on their enhanced optical absorption and scattering properties. In this study, the optical extinction, absorption, and scattering efficiencies were calculated as a function of shape definition, aspect ratio, surrounding medium, and material selection. The discrete dipole approximation method was used, which is known to be a very useful and versatile computational tool for particles with any arbitrary shape. Relative contribution of scattering to the total extinction for the longitudinal mode was found to be significantly dependent on the aspect ratio of the nanorod in a somewhat complex manner, different from a typical linear relationship for the resonance wavelength. A slight elongation of Au nanosphere gives rise to a drastic increase in the relative scattering efficiency, which eventually reaches a maximum and begins to decrease with further increase in the aspect ratio. This is ascribed to the increasing absorptive contribution from the larger imaginary dielectric function of the metal particle in the longer wavelength region where the red-shifted excitation of the longitudinal resonance mode occurs. For transverse mode exhibiting the blue-shift in the resonance peak, on the contrary, the absorption efficiency is relatively enhanced compared to the scattering efficiency with increasing aspect ratio. This is thought to result from the dominant effect of the interband transition present in this wavelength region. Besides the dependence of plasmonic characteristics on the aspect ratio of nanorod, the DDA results for a small change of the end-cap shape and the index of the surrounding medium lead us to conclude that there exist two competing key factors: a weighting factor assigned to the shape parameter and the dielectric function of the metal particle, which control the relative enhancement in the scattering and absorption as well as the linearity of resonance wavelength with regard to the aspect ratio.     

Dynamic light scattering by weakly ionized gels: Effects of inhomogeneities and non-ergodicity

Small angle neutron scattering and light scattering experiments have been performed on partially neutralized poly(acrylic acid) solutions and gels. The structure factor obtained from small angle scattering and static light scattering reveals the absence of significant contribution from large scale inhomogeneities in the gels as soon as the ionization degree exceeds 9·10⁻³. The comparison of the time and ensemble averages of the autocorrelation function of scattered light intensity shows that the gels behave with respect to that experiment as ergodic media.