Microstructural Evolution and Its Effect on Mechanical Properties of Isotactic Polypropylene by Shear Plastic Deformation at Elevated Temperatures

Isotactic polypropylene (iPP) was plastically shear deformed by equal channel angular extrusion (ECAE) at extrusion temperatures varied from 45 to 125°C (25 mm/min). The evolutions of morphology and crystal orientation were studied by reflected optical microscopy (ROM), scanning electron microscopy (SEM), and X-ray diffraction. It was found that the original spherulites were deformed into nearly ellipsoids with their long axis tilted at an angle away from the flow direction. Azimuthal scanning results revealed that two preferred crystal orientations were formed after ECAE. The crystal plasticity was activated by increasing the extrusion temperature, followed by fast rotation of crystallites toward the shear direction. The thermal mechanical analysis (TMA) indicated that low extrusion temperature was favorable to fix the molecular orientation. The iPP samples processed at the investigated temperatures displayed a significant increase in the impact strength, especially for those extruded at 45°C and 65°C. The tensile results revealed a greater elongation at break in the samples deformed at low temperatures (45°C and 65°C) but not in those deformed at high temperatures (85°C or above).     

Integration of correlative Raman microscopy in a dualbeam FIB SEM

We present an integrated confocal Raman microscope in a focused ion beam scanning electron microscope (FIB SEM). The integrated system enables correlative Raman and electron microscopic analysis combined with focused ion beam sample modification on the same sample location. This provides new opportunities, for example the combination of nanometer resolution with Raman advances the analysis of sub‐diffraction‐sized particles. Further direct Raman analysis of FIB engineered samples enables in situ investigation of sample changes. The Raman microscope is an add‐on module to the electron microscope. The optical objective is brought into the sample chamber, and the laser source, and spectrometer are placed in a module attached onto and outside the chamber. We demonstrate the integrated Raman FIB SEM function with several experiments. First, correlative Raman and electron microscopy is used for the investigation of (sub‐)micrometer‐sized crystals. Different crystals are identified with Raman, and in combination with SEM the spectral information is combined with structurally visible polymorphs and particle sizes. Analysis of sample changes made with the ion beam is performed on (1) structures milled in a silicon substrate and (2) after milling with the FIB on an organic polymer. Experiments demonstrate the new capabilities of an integrated correlative Raman–FIB–SEM. Copyright © 2016 John Wiley & Sons, Ltd.     

Study on Properties and Structure of Near Melt Point Extruded High‐Density Polyethylene

The effect of extrusion temperature on the mechanical properties of high‐density polyethylene (HDPE) was examined using solid‐state extrusion (SSE) and melt‐state extrusion (MSE) techniques. Differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) investigations were employed to provide evidence for explaining the relationship between mechanical properties and morphology of extrusion moldings. Extruded from a convergence‐divergence die, compared with samples obtained by MSE, the yield strength of samples obtained by SSE was enhanced in both longitudinal and transverse directions with a ductile failure. The yield strength decreased sharply with increasing extrusion temperature. The maximum longitudinal yield strength of samples extruded at 112°C was 181 MPa with an 87% elongation at break; the corresponding values were 28 MPa and 800% for samples extruded at 140°C (MSE); in the transverse direction the yield strength was 27 MPa with a 101% elongation at break for samples extruded at 140°C, while the maximum yield strength was 51 MPa with a 45% of elongation at break for samples extruded at 116°C. Compared with sheets extruded at 140°C, DSC data shows a 5.3°C increase in melting point, a 9.5°C decrease in melt point width, and a 7.1% decrease in crystallinity for sheets extruded at 112°C. SEM indicates that spherulites predominate in MSE samples, while a preferred orientation of the lamellae along the extrusion direction were mainly produced by SSE.     

Invited Review: DNA-mediated artificial nanobiostructures: state of the art and future directions

DNA (deoxyribonucleic acid)-mediated assembly of nanometer and micrometer scale structures can have a profound impact in the fields of nanoelectronics and nanotechnology. Such structures can also find applications in microelectromechanical systems, hybrid bio-sensors, and the potential to continue the scaling of Moore’s law beyond the 50 nm node. While engineers and scientists have been long aspiring to controllably and specifically manipulate structures at the micrometer and nanometer scale, nature has been performing these tasks and assembling structures with great accuracy and high efficiency using highly specific biological molecules such as DNA and proteins. This paper describes the motivations and fundamentals behind these assembly concepts, with a focus on DNA hybridization-mediated assembly, and presents the state of the art in this field. In addition, new ideas and directions for future research on DNA-mediated assembly of active devices and DNA-based molecular devices are also presented.     

X‐ray nanotomography and focused‐ion‐beam sectioning for quantitative three‐dimensional analysis of nanocomposites

Knowing the relationship between three‐dimensional structure and properties is paramount for complete understanding of material behavior. In this work, the internal nanostructure of micrometer‐size (～10 µm) composite Ni/Al particles was analyzed using two different approaches. The first technique, synchrotron‐based X‐ray nanotomography, is a nondestructive method that can attain resolutions of tens of nanometers. The second is a destructive technique with sub‐nanometer resolution utilizing scanning electron microscopy combined with an ion beam and `slice and view' analysis, where the sample is repeatedly milled and imaged. The obtained results suggest that both techniques allow for an accurate characterization of the larger‐scale structures, while differences exist in the characterization of the smallest features. Using the Monte Carlo method, the effective resolution of the X‐ray nanotomography technique was determined to be ～48 nm, while focused‐ion‐beam sectioning with `slice and view' analysis was ～5 nm.     

Contrasting confocal with defocusing microscale spatially offset Raman spectroscopy

The study compares and contrasts conventional confocal Raman microscopy/spectroscopy (CRM) with a recently developed micrometer scale defocusing spatially offset Raman spectroscopy (micro‐SORS), a method providing a new analytical capability for investigating non‐destructively the chemical composition of subsurface, micrometer‐scale‐thick diffusely scattering layers at depths beyond the reach of CRM. Because of close similarities between the two techniques and comparable embodiment of the instrumentations, but radically different interpretations of data, it is crucially important to recognise which type of method is pertinent to a specific measurement. The distinction comes principally from the nature of sample, whether turbid (micro‐SORS measurement) or transparent (CRM measurement) on the spatial scale of the axial (z‐)scan of the measurement. Which type of sample one deals with may not always be easily recognisable with micro‐scale thick layers, and the study therefore also presents a simple method for suggesting whether CRM or micro‐SORS methodology applies. This test relies on an axial (z‐)scan performed through the sample in both the positive and negative directions from the normal, imaged sample surface position using conventional CRM instrument. The absence or presence of symmetry or asymmetry of the intensity profiles of measured Raman signals around the imaged sample surface position as a function of sample axial displacement then suggests which interpretation could apply. The study paves a way for the development of micro‐SORS as a widely applicable analytical tool deployable on conventional Raman microscopes. Copyright © 2015 John Wiley & Sons, Ltd.     

Mechanics of single pass equal channel angular extrusion of powder in tubes

In the current study powder in tubes (PITs) are processed through single pass equal channel angular extrusion (ECAE), for two different powders by using three different tube materials. Studies were conducted for the first time to understand the processing mechanism of ECAE of PITs. In the case of hard brittle intermetallic magnesium boride (MgB₂) powder, the process was found to primarily involve compaction and shear-sliding of the powder, and localized-deformation of the tube. Reasons for localized-deformation occurring during ECAE were discussed in detail. Compaction efficiency was understood to depend not only on the material of the tube but also on the homogeneity of stress and strain in the composite PIT. Various frictional stresses and mechanisms of localized-deformation were found to be the reasons for stress-strain inhomogeneity. In the case of copper powder, even though localized-deformation occurred, higher inter-particle friction and low yield strength of the powder helped in the complete densification of the powders. PACS 81.20.Ev; 83.50.-V; 07.10.Pz; 62.20.Fe; 74.25.Ld     

Controlling the micro/nanostructure of self-cleaning polymer coating

Polypropylene bio-mimic self-cleaning surfaces with porous micro-nano-binary morphology structures were prepared by a simple casting method. The influence of the cooling process and solvent composition on water contact angle, sliding angles and self-cleaning properties has been investigated. Detailed SEM morphology studies revealed that the polymer used in this work is commercial-grade granular low-density polyethylene (LDPE) forms petal-like crystalline, which are of micrometer scale in length and nanometer scale in thickness. The nano-crystallines on the surface represent a porous three-dimensional micro-nano-binary structure. It was found that a compromise to the film porosity and crystal nano structure is essential for achieving a satisfied self-cleaning surface. Under optimum condition, a water contact angle of 152.2°, and a sliding angle of 1.7° can be obtained using this simple method.     

Rapid fabrication of superhydrophobic surfaces on copper substrates by electrochemical machining

Hierarchical micrometer-nanometer-scale binary rough structures were fabricated on copper substrates by electrochemical machining in a neutral NaCl electrolyte. The rough structures are composed of the micrometer scale potato-like structures and the nanometer scale cube-like structures. After modified by the fluoroalkylsilane, the copper surfaces reached superhydrophobicity with a water contact angle of 164.3° and a water tilting angle less than 9°. This method has a high processing efficiency which can take just 3 s to fabricate the roughness required by the superhydrophobic surface. The effect of the processing time on wettability of the copper surfaces was investigated in this paper. The possible mechanism of the formation of the hierarchical roughness was also proposed, and the wettability of the copper surfaces was discussed on the basis of the Cassie-Baxter theory.     

Identification of polymer matrix yield stress in the wood cell wall based on micropillar compression and micromechanical modelling

Based on a combination of micropillar compression experiments and modelling of the secondary cell wall (cw) using continuum micromechanics, the shear yield stress of the polymer matrix is identified for both normal and compression wood of Norway spruce. It is shown that the model is able to capture the differences in mechanical properties between the two tissues based on the knowledge of composition of the samples, microfibril angle, as well as phase properties on the nanometer scale. By testing an isolated piece of the cell wall with a homogeneous and uniaxial stress field on the micrometer scale and using the micromechanical model to determine average stress fields on the nanometer scale, it is possible to identify the shear yield stress of the polymer matrix in wood, which was found to be in the range of 14.9–17.5 MPa for normal and compression wood. It was shown that this corresponds to a stress in the lignin phase of approx. 17 MPa. This combined study thus demonstrates a new approach for validating multiscale models predicting yield properties with uniaxial experiments at the microscale and measuring phase properties of inhomogeneous materials by a combination of modelling and experimental approaches.     

Aromatic poly(ester carbonate)/poly-(ethylene terephthalate) alloys

When mixtures of poly(ester carbonate) (PEC) and poly(ethylene terephthalate) (PET) containing up to two-thirds of the latter are melt extruded, they produce a single-phase amorphous “alloy.” This alloy is characterized by a sharp, single, composition-dependent glass transition temperature, T_g. When annealed below T_g, the alloy remains unaltered, but when annealed above its T_g, the alloy separates into minute pure-PET crystallites and an amorphous PEC/PET phase. The thermal and dynamic mechanical behavior, crystallization kinetics, and SAXS patterns all strongly suggest the PEC-rich alloys to be solid solutions in which the PET molecules are dispersed individually or in small aggregates containing only a few PET molecules each. Calculations of the interaction parameter and assumed interfacial layer thickness tend to support this suggestion. Use of appropriate solvents allows one to selectively dissolve the PEC and recover from the alloys both PET and PEC in the original purity and molecular weights. Diffusion constants of PET molecules through the amorphous alloys were obtained from studies of PET crystallization above T_g of the alloys. The magnitude of the constants are in the range of expectation. The mechanical properties of the amorphous alloys in the glassy state do not deviate greatly from simple additivity of the respective properties of the parent polymers. However, the melt viscosity of the PEC-rich alloys and their plateau modulus above T show drastic decreases from straight additivity. A qualitative, but not quantitative, explanation of these observations is offered.     

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.     

GISAXS and SAXS studies on the spatial structures of Co nanowire arrays

The spatial structures of magnetic Co nanowire array embedded in anodic aluminium membranes were investigated by grazing incidence small angle X-ray scattering (GISAXS) and conventional small angle X-ray scattering (SAXS) techniques. Compared with SEM observation, the GISAXS and SAXS measurements can get more overall structural information in a large-area scale. In this study, the two-dimensional GISAXS pattern was well reconstructed by using the IsGISAXS program. The results demonstrate that the hexagonal lattice formed by the Co nanowires is distorted (a ≈ 105 nm, b ≈ 95 nm). These Co nanowires are isolated into many structure domains with different orientations with a size of about 2 μm. The SAXS results have also confirmed that the nanopore structures in the AAM can be retained after depositing Co nanowires although the Co nanowires can not completely but only just fill up the nanopores. These results are helpful for understanding the global structure of the Co nanowire array.     

Studies on Rheological Behavior and Structure Development of High‐Density Polyethylene in the Presence of Ultrasonic Oscillations During Extrusion

The effects of ultrasonic oscillations on properties and structure of extruded high‐density polyethylene (HDPE) were studied. The experimental results show that ultrasonic oscillations can improve the surface appearance of the HDPE extrudates; increase the productivity of the HDPE extrudates; and decrease the die pressure, melt viscosity, and flow activation energy of the HDPE. The processing properties of the HDPE improve greatly in the presence of ultrasonic oscillations. Linear viscoelastic properties tests show that dynamic shear viscosity and zero shear viscosity decrease in the presence of ultrasonic oscillations. Ultrasonic oscillations can improve crystal perfection and thermal stability of HDPE. At appropriate ultrasound intensity, ultrasonic oscillations could also increase the mechanical strength of extruded HDPE. The gel permeation chromatography (GPC) results show that at high ultrasound intensity and low rotation speed of extrusion, ultrasonic oscillations causes chain scission of HDPE, which result in a decrease of molecular weight and an increase of melt flow index.     

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.     

Investigation of the Melt‐Crystallization of Polypropylene by a Temperature Slope Method

Abstract

To investigate the in‐situ ordering process of isotactic polypropylene (iPP) from a melt state, a stationary growth front was prepared by the temperature slope crystallization (TSC) method. During the melt‐crystallization, iPP was crystallized into the α‐phase or β‐phase depending on the crystallizing conditions. The mechanism of the melt‐crystallization at the growth front was precisely observed by wide‐angle and small‐angle x‐ray scattering (WAXS and SAXS) using a strong synchrotron beam. In the TSC apparatus, the sample was crystallized in between a heater, controlled to 220°C, and a cooler, cooled by water to 25°C. We define the z‐axis parallel to the temperature gradient. A‐lamellae and B‐lamellae are also defined as those whose lamellar normal are perpendicular and parallel to the z‐axis, respectively. In a sample‐stop (SS) stage before the TSC, the original α‐phase lamellae became thicker, approaching to the melt‐solid boundary by annealing. The annealing process showed that the α‐phase B‐lamellae remained and the SAXS reflection was stronger on the meridian near the melt‐solid boundary in the SS stage. In the beginning of the TSC, the α‐phase B‐lamellae developed as a primary crystallization. During secondary crystallization under high supercooling, the SAXS cross pattern appeared showing that the α‐phase developed both A‐ and B‐lamellae. As the growth direction of A‐lamellae is parallel to the z‐axis, A‐lamellae grow faster than B‐lamellae. By the self‐epitaxial mechanism on the side surface of the A‐lamellae, the B‐lamellae grow on the base of the A‐lamellae. Following appearance of a spontaneous β‐nucleus, the β‐phase lamellae grew preferentially, excluding the α‐phase, and occupied the whole area of the sample. In this case also, A‐lamellae are advantageous to grow because of the growth direction parallel to the z‐axis. As a result, the SAXS β‐phase reflection appeared on the equator.     

Clay‐induced Preferred Orientation in Polyethylene/Compatibilized Clay Nanocomposites

Nanocomposites of the organically modified clay Cloisite^® 15A (CL15A) dispersed in HDPE‐g‐MA were prepared by melt‐compounding. Microcomposites of the same clay with HDPE were also obtained with similar procedures. The spherulitic morphology of the polymer matrix was evidenced by optical microscopy in thin films, whereas the structure of the up to 2‐mm–thick, compression‐molded samples was investigated by WAXD and SAXS. Preferred orientation of both the clay and the HDPE crystallites were evidenced in the microcomposites and, to a greater extent, in nanocomposites, whereas in HDPE and HDPE‐g‐MA control specimens hardly any anisotropy was detected. The degree of orientation of PE crystals increases with CL15A concentration, but also with clay exfoliation, with lower cooling rates and decreasing sample thickness. The orientation of the clay platelets parallel to the compression‐molded surface appears to be determined by the platelets anisotropy and by shear in the mixing and the compression‐molding procedures. In turn, it determines the preferred uniaxial orientation of HDPE crystals, which have their crystallographic a axis orthogonal, while b and c are coplanar, to the sample surface, as already reported in the literature for melt‐crystallized HDPE films with thickness below 0.3 μm. It is proposed that the HDPE orientation results from confined crystallization between parallel clay platelets which are on average less than 0.1 μm apart. Simple models, qualitatively accounting for the observed orientation of HDPE, are discussed. Organized architectures resulting from confined crystallization of the polymer matrix in nanocomposites with appropriate anisotropic fillers may be a general feature, important in determining key properties of these systems.     

Flyscan opportunities in medicine: the case of quantum rattle based on gold quantum dots

The new rapid scan method, Flyscan mode, implemented on the DiffAbs beamline at Synchrotron SOLEIL, allows fast micro‐X‐ray fluorescence data acquisition. It paves the way for applications in the biomedical field where a large amount of data is needed to generate meaningful information for the clinician. This study presents a complete set of data acquired after injection of gold‐cluster‐enriched mesoporous silica nanospheres, used as potential theranostic vectors, into rats. While classical X‐ray fluorescence investigations (using step‐by‐step acquisitions) are based on a limited number of samples (approximately one per day at the DiffAbs beamline), the Flyscan mode has enabled gathering information on the interaction of nanometer‐scale vectors in different organs such as liver, spleen and kidney at the micrometer scale, for five rats, in only a single five‐day synchrotron shift. Moreover, numerous X‐ray absorption near‐edge structure spectra, which are beam‐time‐consuming taking into account the low concentration of these theranostic vectors, were collected.     

Study of Metallocene-Catalyzed Linear Low-Density Polyethylene Solid-State Extrusion: Processing and Mechanical Properties

The effect of extrusion temperature and extrusion drawing ratio (EDR) on the die swell ratio (DSR) and mechanical properties of metallocene-catalyzed linear low-density polyethylene (m-LLDPE) was examined with the application of solid-state extrusion (SSE). Scanning electron microscopy (SEM) was employed to characterize the microstructure and morphology of the extrudates. Extruded from a convergence-divergence die, compared with samples obtained by melt-state extrusion (MSE), the DSR decreases for SSE samples prepared at low extrusion temperature and high EDR. Mechanically strong SSE samples were also obtained at low extrusion temperatures and high EDR. Mechanically strong SSE samples were also obtained at low extrusion temperatures and high EDR. SEM indicates that the microstructures of the MSE samples consist primarily of ring-banded spherulites; the microstructure of the SSE samples was microfibers oriented along the direction of extrusion. The highly oriented microfibers contribute to the improved mechanical strength of the SSE samples.