Correlation between gas transport properties and the morphology/dynamics of crystalline fluorinated copolymer membranes

The crystalline structure, dynamics, and gas transport properties (i.e., the gas permeability, gas diffusion coefficient, and gas solubility coefficient) of poly(tetrafluoroethylene‐co‐perfluoroethylvinylether) (PFA) membranes were systematically investigated via differential scanning calorimetry, wide/small/ultra‐small‐angle X‐ray scattering, and quasielastic neutron scattering measurements. We evaluated the gas transport properties using a constant‐volume/variable‐pressure method. The gas permeability and the gas diffusion coefficient decreased with increasing crystallinity of the PFA membranes at crystallinities below 32%. However, in membranes with a crystallinity of 32% or greater, these parameters depended on the characteristics of the gas molecules, such as their kinetic diameter. The so‐called long spacing period and the thickness of the crystalline/amorphous regions increased with crystallinity according to the small/ultra‐small‐angle X‐ray scattering results. Furthermore, the quasielastic neutron scattering measurements indicated that the scattering law was well fitted to a sum of narrow and broad Lorentzian components. In particular, the narrow components, that is, the local motion of amorphous components and side chains, increased with crystallinity. These results suggest that large gas molecules could pass through the PFA membranes, assisted by the motion in the amorphous region. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45665.     

Photoelectric properties of ABA‐type triblock copolymers designed using fluorine‐containing polyimide macroinitiators with polyhedral oligomeric silsesquioxane

4,4′‐(Hexafluoro‐isopropylidene) diphthalic anhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (6FDA‐TeMPD) was synthesized and reacted with polyhedral oligomeric silsesquioxane (POSS) to form an ABA‐type triblock copolymer by atom transfer radical polymerization. The solid‐state and optical properties of the resulting copolymers were systematically investigated, and their electronic states were analyzed. As the POSS concentration increased, the transparency across the entire wavelength range increased. In the ABA‐type triblock copolymers, a new transition was observed between the highest occupied molecular orbital in POSS and the lowest unoccupied molecular orbital in 6FDA‐TeMPD because of their high molecular size dispersion. Since the refractive index of 6FDA‐TeMPD decreased linearly as the POSS concentration increased, the refractive index of the ABA‐type triblock copolymers of 6FDA‐TeMPD with POSS could be easily controlled. POLYM. ENG. SCI., 57:1207–1213, 2017. © 2017 Society of Plastics Engineers     

Tuneable elastomeric nanochannels for nanofluidic manipulation

Fluidic transport through nanochannels offers new opportunities to probe fundamental nanoscale transport phenomena and to develop tools for manipulating DNA, proteins, small molecules and nanoparticles. The small size of nanofabricated devices and the accompanying increase in the effect of surface forces, however, pose challenges in designing and fabricating flexible nanofluidic systems that can dynamically adjust their transport characteristics according to the handling needs of various molecules and nanoparticles. Here, we describe the use of nanoscale fracturing of oxidized poly(dimethylsiloxane) to conveniently fabricate nanofluidic systems with arrays of nanochannels that can actively manipulate nanofluidic transport through dynamic modulation of the channel cross-section. We present the design parameters for engineering material properties and channel geometry to achieve reversible nanochannel deformation using remarkably small forces. We demonstrate the versatility of the elastomeric nanochannels through tuneable sieving and trapping of nanoparticles, dynamic manipulation of the conformation of single DNA molecules and in situ photofabrication of movable polymeric nanostructures.     

Preparation of poly(1,4‐cyclohexylenedimethylene phthalate)s and their use as modifiers for aromatic diamine‐cured epoxy resin

Poly(1,4‐cyclohexylenedimethylene phthalate) s, prepared by the reaction of phthalic anhydride and 1,4‐cyclohexane dimethanol (35/65 or 73/27 mol % cis/trans or trans alone), have been used to improve the toughness of bisphenol‐A diglycidyl ether epoxy resin cured with 4,4′‐diaminodiphenyl sulfone. The aromatic polyesters include poly(cis/trans‐1,4‐cyclohexylenedimethylene phthalate) (PCP) based on a commercial cyclohexanedimethanol, poly(trans‐1,4‐cyclohexylenedimethylene phthalate) (trans‐PCP) and poly(cis/trans‐1,4‐cyclohexylenedimethylene phthalate) (cis‐rich PCP) prepared from a cis‐rich diol. The polyesters used were soluble in the epoxy resin without solvents and were effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt% of PCP (MW 6400 g mol⁻¹) led to an 80% increase in the fracture toughness (K_IC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism is discussed in terms of morphological and dynamic viscoelastic behaviours of the modified epoxy resin system. © 2000 Society of Chemical Industry     

A high-speed bit synchronization circuit by direct control of the oscillation phase of a VCO

In a large-scale broadband communication system, thousands of high-speed serial data interconnections are used and a bit synchronization circuit (a clock and data recovery circuit) is required in each of the receiver side interconnection circuits. In this paper, the requirements and the implementation of a bit synchronization circuit for the interconnection are considered, and one solution is proposed. In the proposed circuit, the oscillation phase of a VCO is directly controlled by the trigger signal extracted from the input data. Synchronization capture is quick and the circuit is applicable to burst signals. The circuit tolerates jitter and phase variation of the incoming data. The circuit requires no external components, and is suitable for an integrated circuit. The circuit was implemented using a 0.5 μm CMOS process and the data recovery operation from a 440 Mbps pseudo-random pattern was confirmed. Data acquisition is accomplished within three clock periods from 440 Mbps burst data. © 1998 Scripta Technica, Electr Eng Jpn, 125(2): 35–43, 1998     

Direct Enantioselective Three‐Component Kabachnik–Fields Reaction Catalyzed by Chiral Bis(imidazoline)‐Zinc(II) Catalysts

A direct three‐component reaction of aldehydes, amines and diaryl phosphites was catalyzed by a zinc(II) complex of 1,3‐bis(imidazolin‐2‐ly)pyridine (pybim) giving the corresponding α‐aminophosphonates in good yield with good enantioselectivity. The reaction was applied to a wide variety of aromatic aldehydes to give products with excellent yields (up to 99%) and enantiomeric excesses (up to 93% ee).     

Organocatalytic Enantioselective Decarboxylative Addition of Malonic Acids Half Thioesters to Isatins

The organocatalytic enantioselective decarboxylative addition of malonic acids half thioesters to isatins using a squaramide catalyst afforded the products with high enantioselectivity. These products are key intermediates in the synthesis of 3‐substituted 3‐hydroxy‐2‐oxindole derivatives. The first enantioselective synthesis of (−)‐flustraminol B has been accomplished.     

Simultaneous B-M-mode scanning method for real-time full-range Fourier domain optical coherence tomography

High-speed complex full-range Fourier domain optical coherence tomography (FD-OCT) is demonstrated. In this FD-OCT, the phase modulation of a reference beam (M scan) and transversal scanning (B scan) are simultaneously performed. The Fourier transform method is applied along the direction of the B scan to reconstruct complex spectra, and the complex spectra comprise a full-range OCT image. Because of this simultaneous B-M-mode scan, the FD-OCT requires only a single A scan for each single transversal position to obtain a full-range FD-OCT image. A simple but slow version of the FD-OCT visualizes the cross section of a plastic plate. A modified fast version of this FD-OCT investigates a sweat duct in a finger pad in vivo and visualizes it with an acquisition time of 27 ms.     

Room temperature aging behavior of Ti-Nb-Mo-based superelastic alloys

The effect of room temperature (RT) aging on the superelasticity of Ti-Nb-Mo-based superelastic alloys is investigated. The results show that annealing at relatively low temperatures such as 973 K after severe cold rolling results in poor resistance to the effect of RT aging. The transformation stress increases considerably due to the formation of an isothermal ω phase at RT. Addition of Sn is partially effective in suppressing the RT aging effect in the specimens annealed at 973 K. The RT aging effect is suppressed by increasing the annealing temperature, due to the annihilation of lattice defects or non-equilibrium vacancies introduced during cold rolling, which are responsible for accelerating the diffusion process, however, superelasticity is reduced by annealing at higher temperatures, due to a decrease in the critical stress for slip deformation (σ_CSS). The specimen annealed at 1173 K followed by aging at 773 K exhibits stable superelasticity with a high resistance to the effect of RT aging. Annealing at 1173 K causes the annihilation of lattice defects or non-equilibrium vacancies, while aging at 773 K induces precipitation of the α phase, which in turn causes an increase in σ_CSS, and further enhances the resistance to the RT aging effect by enriching the matrix with β-stabilizing elements.