Yuta Hikima

Unprecedented Development of Ultrahigh Expansion Injection-Molded Polypropylene Foams by Introducing Hydrophobic-Modified Cellulose Nanofibers

Herein, an ultrahigh 18-fold expansion of isotactic polypropylene (iPP)/cellulose nanofiber (CNF) nanocomposite foams was achieved for the first time using a core-back foam injection molding technique. It was found that CNFs were well dispersed and aligned along the cell wall in the core-back direction. Interestingly, the formations of a hybrid shish-kebab of CNFs and classic shish-kebab of PP were simultaneously achieved in the PP/CNF composites. Finally, we proposed that the combination of local strong melt strength, probably resulting from the strong alignment of CNFs and subsequent formation of hybrid shish-kebab structures, and weak melt strength in the unreinforced PP melt might be the driving force for remarkably enhancing the PP foamability.

Si-based infrared optical filters

Abstract. Pyramidal silicon nanospikes, termed black-Si (b-Si), with controlled height of 0.2 to 1  μm, were fabricated by plasma etching over 3-in wafers and were shown to act as variable density filters in a wide range of the IR spectrum 2.5 to 20  μm, with transmission and its spectral gradient dependent on the height of the spikes. Such variable density IR filters can be utilized for imaging and monitoring applications. Narrow IR notch filters were realized with gold mesh arrays on Si wafers prospective for applications in surface-enhanced IR absorption sensing and “cold materials” for heat radiation into atmospheric IR transmission window. Both types of filters for IR: spectrally variable and notch are made by simple fabrication methods.

Orientational Mapping Augmented Sub-Wavelength Hyper-Spectral Imaging of Silk

Molecular alignment underpins optical, mechanical, and thermal properties of materials, however, its direct measurement from volumes with micrometer dimensions is not accessible, especially, for structurally complex bio-materials. How the molecular alignment is linked to extraordinary properties of silk and its amorphous-crystalline composition has to be accessed by a direct measurement from a single silk fiber. Here, we show orientation mapping of the internal silk fiber structure via polarisation-dependent IR absorbance at high spatial resolution of 4.2 μm and 1.9 μm in a hyper-spectral IR imaging by attenuated total reflection using synchrotron radiation in the spectral fingerprint region around 6 μm wavelength. Free-standing longitudinal micro-slices of silk fibers, thinner than the fiber cross section, were prepared by microtome for the four polarization method to directly measure the orientational sensitivity of absorbance in the molecular fingerprint spectral window of the amide bands of β-sheet polypeptides of silk. Microtomed lateral slices of silk fibers, which may avoid possible artefacts that affect spectroscopic measurements with fibers of an elliptical cross sections were used in the study. Amorphisation of silk by ultra-short laser single-pulse exposure is demonstrated.

Near-Infrared Spectroscopic Evaluation of the Water Content of Molded Polylactide under the Effect of Crystallization

During melt processing, the moisture inside polylactide (PLA) easily induces hydrolysis, which deteriorates the mechanical and thermal properties of the product. The state of dryness of resin pellets must be monitored to prevent PLA hydrolysis. In this study, near-infrared (NIR) spectroscopy was applied to measure water content in PLA. In addition, the shape of the NIR spectrum is also affected by crystallization, which could lead to a reduction in the accuracy of evaluating the water content. The objective of this research is to construct a robust model for estimating the water content with varying dispersive extents of crystallization. Two methods for estimating water content measured during a drying process were conducted: the integration of absorbance and partial least squares (PLS) regression were conducted to estimate the water contents in PLA considering the effect of crystallization. The slope of the calibration line of the water content obtained from integrating absorbance varied between PLA with different crystallinities. This is due to the overlap between the NIR band of water and that of PLA crystal in the range of 5100–5400 cm−1. We found that the shape of the NIR spectrum was changed by crystallization, and the crystallinity, compared to the thickness of lamellae, was the dominant factor determining such a change of NIR spectra. The PLS model of water content constructed from only amorphous PLA showed large error of estimation in crystallized PLA. In contrast, the PLS model constructed from both amorphous and crystallized PLA estimated the water contents with lower errors. This was because latent variables obtained from both amorphous and crystallized PLA cancelled the effect of crystallization on NIR spectra.

Microcellular foam injection molding with cellulose nanofibers (CNFs)

Cellulose nanofibers (CNFs) nanocomposites polypropylene foams are prepared by microcellular foam injection molding with core-back operation. The modified CNFs were blended with isotactic-polypropylene (i-PP) at different CNFs weight percentages and foamed to investigate the effect of CNFs on cell morphology. CNFs in i-PP increased the elastic modulus and induced a strain hardening behavior. CNFs also shifted the crystallization temperature of i-PP to higher temperature and enhanced crystallization. With these changes in rheological and thermal properties, CNFs could reduce the cell size and increase the cell density of the foams. By adjusting the core-back timing i.e., foaming temperature, the closed cell and the nano-fibrillated open cellular structure could be produced. The flexural modulus and bending strength of foams were measured by three point flexural tester. The flexural modulus and bending strength were increased as the CNFs content in i-PP was increased at any foam expansion ratio.

Optical and thermal characterization on micro-optical elements made by femtosecond laser writing

Femtosecond laser polymerization of photonic crystals (PhCs) and diffractive micro-optical elements which can be easily integrated into complex 3D geometries of micro-fluidic chips is analysed in IR spectral domain. Thermal properties of such 3D optical elements and patterns were investigated by thermal imaging, IR spectroscopy and a heat-wave method using absorption-heating with visible light. Thermal imaging allows a simple in situ judgement on a 3D fabrication quality of photonic crystals and is simpler compared with scanning electron imaging. Photonic stop gaps at IR spectral range were clearly observed and IR mapping at the specific spectral wavelength reveals spatial uniformity of PhCs. Potential to use IR imaging with spectral IR plasmonic filters for sensor applications is discussed.

Author correction: Orientational Mapping Augmented Sub-Wavelength Hyper-Spectral Imaging of Silk

A correction to this article has been published and is linked from the HTML version of this paper. The error has been fixed in the paper.

Evolution of cellular morphologies and crystalline structures in high-expansion isotactic polypropylene/cellulose nanofiber nanocomposite foams

Herein, the development of cell morphology and crystalline microstructure of injection-molded isotactic polypropylene/cellulose nanofiber (PP/CNF) composite foams with 2–10-fold expansion ratios was investigated through scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD), and small-angle X-ray scattering (SAXS). Compared with isotactic polypropylene (iPP) foams, the added CNF improved the cell morphology and resulted in a great reduction in cell size. Additionally, the PP lamella orientation and crystal type were notably altered during the core-back FIM process. As the expansion ratio increased, the original isotropic lamellae in the iPP foams were transformed into an oriented lamellar structure and then further transformed into a typical shish-kebab structure, while hybrid shish-kebab structures were simultaneously generated in the high-expansion PP/CNF nanocomposite foams. Accordingly, the highest content of β-crystals was observed in the low-expansion iPP foams. In contrast, the β-crystal content in PP/CNF composites decreased monotonously as the expansion ratio increased, which resulted from the combined effects of CNFs nucleating ability for α-crystals and the more dominant extensional flow effect assisted by the added CNF.

Supercritical CO2 assisted electroless plating on polypropylene substrate-effect of injection speed on adhesive force of metal to polymer

The aqueous plating solution cannot be diffused into a plain polypropylene (PP) substrate and consequently Ni-P metal layer cannot be formed by electroless plating on the PP substrate with a satisfied degree of adhesive force unless the hydrophilicity of the substrate surface was increased. A block copolymer PP-b-polyethylene oxide (PP-b-PEO) was used to increase the hydrophilicity of the surface and the adhesive force of the metal layer to the satisfactory level. Our previous study showed the morphology of PP-b-PEO domain near the surface of substrate strongly affected the adhesiveness of the metal layer to the substrate. The degrees of elongation and orientation of the PP-b-PEO domains in PP matrix were the key factors of determining the thickness of the metal-PP composite layer and the resulting adhesive strength. In this study, the effect of injection molding condition on the degrees of elongation and orientation was investigated: PP/PP-b-PEO blend substrates were prepared by injection molding at diff...