Mechanisms of orientational and photoelastic birefringence generation of methacrylates for the design of zero–zero‐birefringence polymers

The intrinsic birefringence Δn⁰ and photoelastic coefficient C of poly(methyl methacrylate), poly(2,2,2‐trifluroethyl methacrylate), poly(phenyl methacrylate), and poly(2,2,3,3,3‐pentafluorophenyl methacrylate) were determined. We categorized these methacrylate polymers into four birefringence‐types, even though their molecular structures differed only by the substituents on the side chains. Based on the results of Δn⁰ and C, novel polymers that exhibit neither orientational nor photoelastic birefringence, i.e., zero–zero‐birefringence polymers, were designed and synthesized by quaternary copolymerization system. Furthermore, we confirmed that the mechanisms of orientational birefringence and photoelastic birefringence generation were different in these methacrylate polymers. The conformation of the repeat unit of the polymers was nearly constant during the generation of orientational birefringence. In contrast, the conformation of the repeat unit of the polymers changed during the generation of photoelastic birefringence in the glassy state. These findings demonstrated the reasonability of evaluating orientational and photoelastic birefringence separately, as well as the adequacy of the classification of polymers into four birefringence‐types. Given these results and the fact that zero–zero‐birefringence polymers could be prepared successfully by four‐birefringence type monomers, we demonstrated the reasonability of the method for designing the zero–zero‐birefringence polymers. POLYM. ENG. SCI., 55:1330–1338, 2015. © 2015 Society of Plastics Engineers     

Development of co-continuous structure in liquid crystalline polyester

We investigated liquid crystallization of liquid crystalline polyester BB-5 during isothermal annealing by digital high-fidelity microscope and light scattering. A liquid crystalline spherical domain having a radius of micrometers appeared by annealing at around 180 °C. The domain grew dendritically in all directions. Neighboring liquid crystalline regions coalesced and then interconnected. The interconnected structure changed to a co-continuous two-phase structure with increasing ordering of the liquid crystalline phase, and the interface between the liquid crystalline phase and the isotropic phase became smoother over time. Liquid crystallization stopped before volume filling the whole space, and the liquid crystalline phase and isotropic phase coexisted. The liquid crystalline region became narrower with an increase in the temperature of the liquid crystallization. Such structural development is different from the liquid-liquid phase separation via spinodal decomposition, and it may be attributed to the segregation of non-liquid crystallizable low molecular weight molecules from the growth front by fractionation of the molecular weight distribution during the liquid crystallization in terms of the instability of the diffusion-controlled interface.     

Modern interpretation on the high-stretching of natural rubber attained by the classic ‘racking’ method

To investigate the mechanism of high elongation of natural rubber attained by the ‘racking method’, a strip of smoked-sheet was elongated up to 150 times in length, by stretching rapidly at room temperature and forcing to shrink at 75-80 °C repeatedly. On X-ray diffraction, a typical fibre pattern with an amorphous ring appeared already at ×10 (stretch ratio=10). The degree of crystallinity increased to the level of 17-18% at ×20 and turned to decrease after ×60, but the degree of crystallite orientation reached at a high level already at ×10 and did not change significantly and the half-height width of reflection profiles stayed almost at a constant level, while the Young's modulus increased up to ca. 300 MPa at ×100 and then fell rather discontinuously. It was assumed that some fractions of chain segments between entanglements were gradually broken in each step of stretching operation, rather than disentangled and slipped.     

Effect of 8 MeV electron irradiation on electrical properties of CuInSe2 thin films

Radiation damages due to 8 MeV electron irradiation in electrical properties of CuInSe₂ thin films have been investigated. The n-type CuInSe₂ films in which the carrier concentration was about 3×10¹⁶ cm⁻³, were epitaxially grown on a GaAs(0 0 1) substrate by RF diode sputtering. No significant change in the electrical properties was observed under the electron fluence <3×10¹⁶ e cm⁻². As the electron fluence exceeded 10¹⁷ e cm⁻², both the carrier concentration and Hall mobility slightly decreased. The carrier removal rate was estimated to be about 0.8 cm⁻¹, which is slightly lower than that of III–V compound materials.     

Network formation and swelling behavior of photosensitive poly(vinyl alcohol) gels prepared by photogenerated crosslinking

Poly (vinyl alcohol) with pendent styrylpyridinium groups (SbQ) is insolubilized by photoirradiation. An association takes place in SbQ groups. The association of polymer chains becomes marked with increasing the number of SbQ groups. Mainly intermolecular crosslinks were formed. Transparent and homogeneous macrogels consisting of several intermolecular crosslinks are obtained. The proportion of the free water to the bound water in PVA-SbQ gels was 3.3?2.9 despite of the large change in conversion of photodimerization of SbQ groups, x=0.27?0.58. The water uptake after swelling of the gels in water increased 6–27 times compared to the original weight at pH=7. The higher the degree of photocrosslinking, the lower was the degree of swelling. The water diffusion coefficients, D, were (2.2?5.8) × 10^?5 cm² S^?1 for a 88% saponified PVA with 1 . 3 mol% SbQ groups. The volume of the gel increased discontinuously about 10-fold for the 99% saponified PVA with 0 . 096 mol% SbQ and 51% water (49% acetone). The acetone concentration at the transition decreased with increasing the degree of saponification of the PVA.     

Dynamic compensation by fusing a high-speed actuator and high-speed visual feedback with its application to fast peg-and-hole alignment

This paper presents a dynamic compensation concept to grapple with the dynamic defects of a traditional robot arm, especially while performing high-speed endpoint regulations. The proposed high-speed dynamic compensation concept offers a new point of view for cooperating with a traditional manipulator to realize highly dexterous performance of manipulations. The concept is realized through adoption of a high-speed light-weight actuator as well as endpoint closed loop configured high-speed cameras. The dynamic compensation is analyzed experimentally with 1000 Hz visual feedback and a high-speed finger for a robot arm in the case of one degree of freedom. The advantage of the proposed approach is that the modeling for the robot system’s dynamics is not needed, whereas it is necessary and trivial in order to realize high-speed regulations by traditional approaches. Thus, the control issue becomes easier with the proposed approach. As an application for this concept, fast peg-and-hole alignment with large position and attitude uncertainty is studied. The alignment algorithm is based on a visual compliance strategy. Alignment experiments show that with the proposed concept of dynamic compensation as well as visual compliant motion control, robust and fast convergence was realized for most cases.     

Development of three-electrode type micro-electrochemical reactor on anodized aluminum with photon rupture and electrochemistry

Photon rupture with a focused single pulse of pulsed YAG-laser irradiation was used to fabricate an aluminum electrochemical micro-reactor. Porous type anodic oxide film formed on aluminum specimens was irradiated in solutions with a pulsed Nd-YAG laser beam through a convex lens to fabricate micro-channels, micro-electrode, and through holes (for reference electrode, solution inlet, and outlet). During irradiation, specimens were moved by a computer controlled XYZ stage. After irradiation, the surface of the micro-channel and through hole were again treated to form anodic oxide film and the surface of the micro-electrode was treated electrochemically to provide an Au layer. The calculated volume of the micro-reactor including micro-channel and through holes is about 1.5 μl. The cyclic voltammogram of the micro-electrochemical cell was measured in K₃Fe(CN)₆/K₄Fe(CN)₆ with both static and flowing solution at different scanning rates. The anodic and cathodic peak currents were measured and the values depended on scanning rate and ion concentration when the solution was static. With the flowing solution, limiting currents were observed and the anodic limiting current was increased with the cubic root of the solution flow rate.