Microfocus small‐angle X‐ray scattering investigation of the skin–core microstructure of lyocell cellulose fibers

Skin–core microstructures in hydrated lyocell cellulose fibers were investigated using microfocus small‐angle X‐ray scattering (SAXS). Both single fibers and fiber cross sections were observed. In all the fibers studied, a thin skin layer was observed in which the voids were smaller in cross section and better oriented than those in the core. The division between skin and core may not be sharp. A draw ratio of 0.80 gave fibers with voids that were shorter, larger in cross section, and more misoriented than the fibers produced with a draw ratio of 1.68. In contrast, there was little difference in void structure between samples coagulated in water and in 25% amine oxide aqueous solution. The results are explained in the context of the spinodal decomposition, which is thought to occur during coagulation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2799–2816, 2002; DOI 10.1002/app.10256     

Imaging of Fluid Dynamics in a Structured Packing Using X‐ray Computed Tomography

For the investigation of fluid dynamics from computed tomography (CT) images, an evaluation method was developed that enables data acquisition directly from the recorded CT images. A segmentation algorithm was implemented in Matlab to assign every component a specific gray value. A comparison of weight experiments with CT scans and following segmentation demonstrates the good accuracy of this method. The liquid holdup in different Mellapak 500.Y packings was determined through CT measurements and compared to predictive correlations from the literature. Three‐dimensional visualizations of short packing sections enable an evaluation of the liquid distribution and the flow morphology of the liquid in the packing. The common assumption of an evenly wetted packing surface with a constant liquid film thickness could not be proved.     

X‐ray diffraction studies on reverse‐annealed polyethylenes

Linear low and high density polyethylene sheets were compression molded and crystallized at a 5–10°C/min cooling rate. Parts of the sheets were annealed at different temperatures up to 2°C below the melting temperature. The small angle X‐ray scattering (SAXS) and the wide angle X‐ray scattering intensities of the annealed samples were studied. SAXS intensities showed particle scattering with a bimodal size distribution. The estimated radii of gyration were 15–17 nm and 5–7 nm, respectively. The crystallinity and the radius of gyration increased slightly with increasing annealing temperature for some samples; others did not show any change. No peaks characteristic of intercorrelated lamellar crystallinity in the SAXS intensities developed during the annealing. The original broad peak of high density polyethylene disappeared from the SAXS recordings on annealing. The length of the perfect chain versus melting temperature was calculated by the Thomson‐Gibbs formula and Flory's concept of melting temperature depression where methyl groups and tertiary carbon atoms at the branches were regarded as second components (solvent). Linear relationships were found for both cases. Experimental data for a linear low density polyethylene obtained from the literature were in between the two functions. A lamellar model of crystallization corresponding to the data is proposed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 340–349, 2001     

X‐ray pole figures to assess orientation in PVC sheets

A series of X‐ray pole figures were obtained from oriented and unoriented rigid polyvinyl chloride sheets. From these, information about crystallite orientation in uniaxially and biaxially drawn sheets stretched at 90°C was obtained. Uniaxial orientation produced two crystallite orientations with the extent of orientation increasing with draw ratio; for biaxial samples the chain direction (c) was distributed uniformly in the plane of the sheet, with the planar orientation improving as draw ratio increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 528–535, 2007     

About the Lorentz correction used in interpretation of small‐angle X‐ray scattering data of semicrystalline polymers

Lorentz correction is used to correct the intensities of X‐ray scattering of single‐crystal diffractometry in order to recalculate intensities to obtain structure factors. This correction reduces the intensities to zero at zero diffraction angle. Small‐angle scattering is used to study the dimensions of heterogeneities in polymeric materials. The scattering intensities at a near to zero scattering angle originate partly from periodic systems (reciprocal lattice) and partly from dispersed particle systems. Periodic systems should result in individual Gaussian or Lorentzian peaks with the position of a peak maximum depending on the length of the periodicity. Particle scattering results in a Gaussian peak centered at zero scattering angle. The effect of the Lorentz correction on the interpretation of small‐angle X‐ray scattering data is shown for some semicrystalline polyethylenes (high‐density, linear low‐density, and low‐molecular‐weight waxy polyethylenes). The data are compared to those for amorphous block copolymers (styrene–butadiene), in which there is a periodic system with homogeneous lamellar thickness. Lorentz correction destroys the characteristics of the particle scattering and can be applied only for periodic systems. It should not be used to produce a peak on scattering data, which do not show periodicity (peaks) without correction. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 358–366, 2001     

X‐ray photoelectron spectroscopic study of silk fibroin surface

X‐ray photoelectron spectroscopy (XPS) has been used to probe the nature of silk fibroin surface, in particular the tyrosine content and sulfur species on the surface. The iodine labelling treatment of silk, followed by XPS surface analysis, reveals that silk fibroin has a tyrosine‐enriched surface, and that there are sulfur‐containing amino acids present on the surface, mainly occurring in the S⁶⁺ component. UV/ozone treatment modifies/removes the surface tyrosine‐ and sulfur‐containing species. © 2002 Society of Chemical Industry     

Surface structure of isotactic polypropylene by X‐ray diffraction

With the glazing angle incidence of an X‐ray beam, the surface structure of compression molded isotactic polypropylene film was investigated by X‐ray diffraction. A comparison of the crystallinities between the surface and the bulk was made for films annealed in air at different temperatures and times. The crystallinity was lower for the surface compared with the bulk irrespective of annealing conditions. A drastic change in crystallinity occurred up to depths of several micrometers from the surface, and crystallinity decreased near the surface. The apparent crystallite sizes were smaller for the surface. This showed that crystal growth was restricted near the surface because of localized defects (including chain ends), and high chain mobility. Annealing at higher temperatures induced surface oxidation, which also decreased the surface crystallinity. The residual stress near the surface, attributable to quenching from the melt, was also detected by this method.     

Sillimanite‐mullite transformation observed in synchrotron X‐ray diffraction experiments

High‐resolution synchrotron powder X‐ray diffraction (XRD) experiments were conducted to clarify the transformation of sillimanite to mullite (mullitization) and determine the mullitization temperature (T_c). We were able to distinguish sillimanite and mullite in the XRD patterns, despite their very similar crystallographic parameters, and to detect the appearance of small mullite peaks among sillimanite peaks. Analysis of the Johnson‐Mehl‐Avrami (JMA) equation for mullitization ratio (ζ) revealed that at temperatures T≥1240°C the mullitization had the same kinetics. The activation energy E at T≥1240°C obtained from the Arrhenius plot was 679.8 kJ mol^?1. In analysis using a time‐temperature‐transformation diagram for mullitization, a mullitization curve of ζ=1% can be described as where t is time, n is a reaction‐mechanism‐dependent parameter determined as 0.324 by JMA‐analysis, k₀ is the frequency factor, E_A is the activation energy for atomic diffusion, and represents the activation energy for nucleation. The results of fitting the data to this equation were T_c=1199°C, A=3.9×10⁶ kJ mol^?1 K^?2, E_A=605 kJ mol^?1, and k₀=3.65×10¹⁵. We conclude that the boundary between sillimanite and mullite+SiO₂ in the phase diagram is ~1200°C.     

Peak‐fitting analysis of cotton fiber powder X‐ray diffraction spectra

The precision and accuracy of diffraction peak positions resolved from the powder X‐ray diffraction spectra of cotton fibers by means of the residuals peak‐fitting procedure of a commercial peak‐fitting software package (PeakFit®) was investigated to explore the potential of such programs in providing reliable data that are not readily apparent in diffuse X‐ray spectra. Each intensity spectrum was fitted by employing a Gaussian function as the peak profile. The precision of 15 pairs of the resolved diffraction peaks is 0.0017 mm; 9 of the 15 pairs fall into the 99% confidence interval. The precision in 2θ of four commonly identified peaks through four independent fittings is from 0.002 to 0.014°. The 2θ accuracy of the resolved peaks is good in comparison to data calculated for both the traditionally accepted and the more recently revised concepts of the cellulose I crystal structure. A peak resolved at about 15.3° may be attributed to the triclinic crystal structure component of cellulose I. Although distinct peaks are not readily apparent in the diffuse spectrum of cellulose, peak‐fitting procedures may provide additional data for structure determination. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2019–2024, 2004     

Method for Direct Determination of Glassy Phase Dissolution in Hydrating Fly Ash‐Cement System Using X‐ray Diffraction

A method for quantitative X‐ray diffraction analysis is developed for direct determination of the glassy phase content of fly ash in a hydrating binary blend of cement and low‐calcium, siliceous fly ash. The intensity contributions of the unhydrated glassy phase of fly ash and the amorphous reaction products to the intensity pattern of the total amorphous phase in the hydrating binary blend are obtained by decomposition of the total intensity signature as a sum of component pseudo Voigt (PV) peaks. An experimental program involving binary blends with three different low calcium siliceous fly ashes and two different curing temperatures is reported. The centers of the component PV peaks of the fly ash glassy phase fitted to the overall intensity pattern are found to be invariant. The glassy phase content of hydrating binary blends determined from the XRD method were found to agree well with the values obtained from a selective dissolution method.     

Experimental methods in chemical engineering: X‐ray photoelectron spectroscopy‐XPS

X‐ray photoelectron spectroscopy (XPS) is a quantitative surface analysis technique used to identify the elemental composition, empirical formula, chemical state, and electronic state of an element. The kinetic energy of the electrons escaping from the material surface irradiated by an x‐ray beam produces a spectrum. XPS identifies chemical species and quantifies their content and the interactions between surface species. It is minimally destructive and is sensitive to a depth between 1–10nm. The elemental sensitivity is in the order of 0.1 atomic %. It requires ultra high vacuum ( Pa) in the analysis chamber and measurement time varies from minutes to hours per sample depending on the analyte. XPS dates back 50 years ago. New spectrometers, detectors, and variable size photon beams, reduce analysis time and increase spatial resolution. An XPS bibliometric map of the 10 000 articles indexed by Web of Science^[1] identifies five research clusters: (i) nanoparticles, thin films, and surfaces; (ii) catalysis, oxidation, reduction, stability, and oxides; (iii) nanocomposites, graphene, graphite, and electro‐chemistry; (iv) photocatalysis, water, visible light, and ; and (v) adsorption, aqueous solutions, and waste water.     

Hydrolytic aging of polypropylene studied by X‐ray photoelectron spectroscopy

X‐ray photoelectron spectroscopy (XPS) was used to study the hydrolytic aging of polypropylene according to the pHs of degrading buffer solutions and the time of aging. The study was concentrated over periods of 3, 6, and 9 months for values of pH close to the real environments of use of the material (pH of 6, 7, and 8). The polypropylene underwent an oxidation of its polymeric matrix, independently of the range of pH values, by the production of C? OH, C?O, and O?C? O groups. These chemical functions were observed in high resolution XPS spectra around C1s and O1s peaks. Beginning with these results and from mechanisms of (photochemical, thermal, and others) aging proposed in the literature, it was then possible to propose mechanisms of hydrolytic ageing of polypropylene. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3830–3838, 2004     

Recent developments in polymer applications of synchrotron small‐angle X‐ray scattering

Synchrotron radiation facilities have been established and become very familiar in the polymer community not only from academic but also industrial viewpoints. It is not so unusual now to conduct simultaneous measurements of small‐angle X‐ray scattering (SAXS) with other techniques such as wide‐angle X‐ray scattering, stress–strain, light scattering, and so forth. New techniques have also been established and have become more familiar in recent years. In this review, recent developments in polymer applications of synchrotron SAXS are summarized. Instrumental developments and progress in data analyses are reviewed from the following aspects: ultra‐small‐angle X‐ray scattering, anomalous SAXS, X‐ray photon correlation spectroscopy, new types of simultaneous measurements, grazing‐incidence SAXS, new trends in nanoparticle analyses and industrial applications. © 2016 Society of Chemical Industry     

Quantifying intermediate‐frequency heterogeneities of SOFC electrodes using X‐ray computed tomography

The electrodes in solid oxide fuel cells (SOFCs) consist of three phases interconnected in three dimensions. The volume needed to describe quantitatively such microstructures depends on several lengths scales, which are functions of materials properties and fabrication methods. This work focuses on quantifying the volume needed to represent “intermediate frequency” heterogeneities in electrodes of a commercial SOFC using X‐ray computed tomography (CT) over two different length scales. Electrode volumes of 150 μm × 150 μm × 9 μm were extracted from a synchrotron‐based micro‐CT data set, with 1³ μm³ voxels. 13.6 μm × 19.8 μm × 19.4 μm of the cathode and 26.3 μm × 24.8 μm × 15.7 μm of the anode were extracted from laboratory nano‐CT data sets, both with 65³ nm³ voxels. After comparing the variation across sub‐regions for the grayscale values from the micro‐CT, and for the phase fractions and triple phase boundary densities from the nano‐CT, it was found that the sub‐region length scales needed to yield statistically similar average values were an order of magnitude larger than those expected to capture the “high frequency” heterogeneity related to the discrete nature of the three phases in electrodes. The challenge of quantifying such electrodes using available experimental methods is discussed.     

Real‐time wide‐angle X‐ray diffraction during polyethylene blown film extrusion

Real‐time wide‐angle X‐ray diffraction (WAXD) measurements during blown film extrusion of low‐density polyethylene are reported in this study. WAXD patterns were obtained at different axial positions in the blown film line starting from a location near the die and extending up to the nip‐roller. The X‐ray diffraction patterns from the bubble were analyzed for crystalline growth along the bubble. From the evolution of (110) and (200) peaks, it is evident that the crystallization process starts near the frost‐line height (FLH), shows a steep growth immediately past the FLH, and then plateaus at higher axial distances near the nip‐rolls. The real‐time crystallinity profiles obtained from WAXD were consistent with those measured using real‐time Raman spectroscopy. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Thermal,morphological, and X‐ray study of polymer‐clay nanocomposites

Synthesis and characterization of polymer nanocomposites consisting of diglycidyl ether of bisphenol‐A with inorganic as well as organically modified nanosized clay fillers, for example, vermiculites and montmorillonite, obtained from trade, are studied. Confirmations of intercalation and exfoliation characteristics of these fillers into the cured epoxy resin matrix have been investigated by wide angle X‐ray diffraction studies. Scanning electron microscopy and atomic force microscopy techniques have been adopted to assess the nature of filler dispersion, size of the agglomerates, and the polymer‐filler adhesion. While significant improvement in the mechanical properties (i.e., tensile, flexural strength, and modulus) has been observed, the thermo‐oxidative stability of the composites measured by thermogravimetric analysis showed only marginal improvement. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Correlative Studies on Sintering of Ni/BaTiO3 Multilayers Using X‐ray Computed Nanotomography and FIB‐SEM Nanotomograhy

Synchrotron X‐ray computed nanotomography (nCT) and Focused Ion Beam–Scanning Electron Microscope nanotomography (FIB‐nT) were used to characterize baked‐out and sintered nickel (Ni) electrode–Multilayer Ceramic Capacitors. The three‐dimensional microstructures obtained by two different tomography techniques were quantified and correlated. X‐ray nCT is sufficient to reveal the pore characteristics, whereas the FIB‐nT enables the particles in the initial packings to be identified. In the dielectric ceramic layers, pores preferentially orient horizontally in the layer and the regions near the Ni/BT interface are denser than the inner regions. This anisotropy is possibly caused by compressive stress induced during the heating stage.     

X‐ray tomography of feed‐to‐glass transition of simulated borosilicate waste glasses

High‐level waste feed composition affects the overall melting rate by influencing the chemical, thermophysical, and morphological properties of a cold cap layer that floats on the molten glass where most feed‐to‐glass reactions occur. Data from X‐ray computed tomography imaging of melting pellets comprised of a simulated high‐aluminum feed reveal the morphology of bubbles, known as the primary foam, for various feed compositions at temperatures between 600°C and 1040°C. These feeds were formulated to make glasses with viscosities ranging from 0.5 to 9.5 Pa s at 1150°C, which was accomplished by changing the SiO₂/(B₂O₃+Na₂O+Li₂O) ratio in the final glass. Pellet dimensions and profile area, average and maximum bubble areas, bubble diameter, and void fraction were evaluated. The feed viscosity strongly affects the onset of the primary foaming and the foam collapse temperature. Despite the decreasing amount of gas‐evolving components (Li₂CO₃, H₃BO₃, and Na₂CO₃), as the feed viscosity increases, the measured foam expansion rate does not decrease. This suggests that the primary foaming is not only affected by changes in the primary melt viscosity but also by the compositional reaction kinetic effects. The temperature‐dependent foam morphological data will be used to inform cold cap model development for a high‐level radioactive waste glass melter.     

X‐ray crystal structure analysis for CI Disperse Orange 61

The synthesis, crystal structure analysis and characterisation of a monoazo dye, CI Disperse Orange 61, are reported. The dye crystallised in the triclinic system, space group P‐1 with a = 8.859(2), b = 9.899(2), c = 11.417(3)Å, α = 78.51(4)°, β = 70.37(3)°, γ = 80.46(4)°, V = 918.8(4)ų and Z = 2. There is only one molecule in the asymmetric unit. The two phenyl rings are oriented at a dihedral angle of 57.87(20)°. In the crystal structure, intermolecular C–H…N hydrogen bonds link the molecules into centrosymmetric dimers, forming R₂²(30) ring motifs, in which they may be effective in the stabilisation of the structure. The π…π stacking (interactions) between the phenyl rings may further stabilise the structure, with a centroid–centroid distance of 3.741(4)Å.     

Recycled car bumpers' impact resistance investigated by wide‐angle X‐ray diffraction

The recycled polyolefinic product from discarded standard car bumpers collected from Rio de Janeiro suburb shops was characterized by mechanical and wide‐angle X‐ray scattering (WAXS) methods. We found that the recycled plastic mixture is composed mainly of polypropylene (PP), containing ethylene‐propylene‐diene (EPDM) terpolymers and a minor proportion of high‐density polyethylene (HDPE), and is highly resistant to impact. The results were compared with the corresponding data obtained from binary and ternary blends of virgin PP, EPDM, and HDPE. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 999–1004, 2000