Stereo-Preference in the degradation of the erythro and threo isomers of β-O-4-type lignin model compounds in oxidation processes. part 2: In the reaction with hydroxyl and oxyl anion radicals under hydrogen peroxide bleaching conditions

We examined which isomer, the erythro or threo, of non-phenolic β-O-4-type lignin model compounds is stereo-preferentially attacked by hydroxyl radical and its conjugate base, oxyl anion radical, generated by the decomposition of hydrogen peroxide in the presence of ferric ion and its precipitates under hydrogen peroxide bleaching conditions. The intrinsic stereo-preference of oxyl anion radical was slightly toward the erythro isomer, while hydroxyl radical had a further smaller stereo-preference. These stereo-preferences can be explained by our prior knowledge that oxyl anion radical preferentially attacks the side-chain of the lignin model compounds rather than the aromatic nucleus. The amount of the degraded lignin model compounds became less great with decreasing pH, but reversely and intensively greater in the pH range below 10. This phenomenon can be attributed to the change in the decomposition mechanism of hydrogen peroxide accompanying the pH variation.     

Crosslinking of poly(vinyl alcohol) and poly(vinyl acetate) using poly(maleic anhydride‐alt−2,4‐dimethyl‐1,3‐pentadiene) as polyfunctional crosslinker and decrosslinking by ozone degradation

Crosslinking and decrosslinking reactions of poly(vinyl alcohol) (PVA) and poly(vinyl acetate) (PVAc) using an alternating copolymer of maleic anhydride and 2,4‐dimethyl‐1,3‐pentadiene (PMAD) as the polyfunctional crosslinker and subsequent ozone degradation are reported. PVA and PVAc are heated at 200 °C for 0.5 to 3 h in the presence of 5 to 30 wt % of PMAD in the solid state to obtain the corresponding crosslinked polymers. The reactions of a hydroxy group of PVA and an acetate group of PVAc with an anhydride group of PMAD slowly proceed to give insoluble polymers with a loose crosslinking structure. Almost no change in the thermal decomposition temperatures and the IR spectra is observed during the crosslinking reactions. The crosslinked PVA produces hydrogels with a high swelling ratio of 500 to 1700%, which are readily degradable during a reaction with ozone in water at 0 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44229.     

Poly(N‐isopropylacrylamide) gel‐based macroporous monolith for continuous‐flow recovery of palladium(II) ions

Macroporous monoliths, composed of thermoresponsive, tertiary‐aminated, and crosslinking monomers, were prepared for continuous‐flow separation of palladium(II) ions. N ‐Isopropylacrylamide was required to form the porous structure in the monoliths, indicating that the mechanism of porous structure formation involved polymerization‐induced phase separation of the poly(N ‐isopropylacrylamide) gel. Tertiary‐aminated monoliths showed adsorption selectivity for palladium(II) ions in hydrochloric media, compared with copper(II) ions. The maximum capacities of the monoliths with tertiary amine contents of 10, 20, 30, and 70 mol % for palladium(II) ions were 0.6, 1.1, 1.3, and 2.3 mmol/g, respectively. Darcy's permeabilities of water through the macroporous monolith were 10^?14 to 10^?13 m², and those were comparable to that through a commercially available membrane filter with a pore size of several micrometers. In the continuous‐flow process, the macroporous monolith with tertiary amine selectively adsorbed palladium(II) ions in the coexistence of copper(II) ions with 10 times higher concentration than the palladium(II) ions. The palladium(II) ions were eluted from the macroporous monolith, and the concentration of palladium(II) ions in the eluate was up to 45 times of that in the feed solution. The average enrichment factor and total recovery percentage of palladium(II) ions were 8.7 times and 95%, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44385.     

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     

Hydrolysis of polyurea under high pressure of carbon dioxide

A chemical decomposition of polyurea (PUA) by hydrolysis under high pressure of carbon dioxide (CO₂) was proposed. The hydrolysis of PUA was carried out at 190 °C for 2 h under 7.0 MPa of CO₂ in the presence of water. The hydrolysis reaction gave white residual solid and water soluble compound. The white residual solid was characterized to be degraded PUA by FT-IR spectrum and elemental analysis. ¹H-NMR spectra of the water soluble compound revealed that the hydrolysis of PUA produced diamine only from repeating unit of PUA, which was a component of PUA. This hydrolysis gave the corresponding diamine for quantitative yields.     

Influence of Relative Position of Gears and Casing Wall Shape of Gear Box on Churning Loss under Splash Lubrication Condition—Some New Ideas

A new rotatable test rig is developed to perform oil churning loss experiments to clarify the influence of the relative position of gears and casing wall shape of gear box under splash lubrication condition. Torque losses are measured and photos are taken using a stroboscope to observe the oil behavior. Based on the test results, it has been confirmed that in addition to the well-known factors, relative position and casing wall shape have significant effects on the churning loss and should be considered in the modeling process, which has been neglected in most previous studies. In this article, the importance of the steady-state oil surface profile (SOSP) is emphasized. New ideas are proposed on how other working conditions such as immersion depth and rotation speed influence the churning loss.     

Role of Cu film texture in grain growth correlated with twin boundary formation

To understand the role of Cu film texture in grain growth at room temperature (RT) in relation to twin boundary formation Cu films were deposited on various barrier materials and the Cu film texture was investigated by X-ray diffraction. Cu grain growth was rapid on a barrierless SiO₂/Si substrate and very slow on a Ta barrier due to strong (1 1 1) texture. The growth rate and the average grain diameter after being kept at RT for up to ∼60 days were maximum at a (2 0 0)_Cu peak to (2 2 2)_Cu peak area ratio of ∼1.0, where {1 1 1}, {1 0 0} and {5 1 1} grains coexisted. Such coexistence of three or more orientations of grains is essential in facilitating Cu grain growth at RT. Similarly, the average twin boundary (TB) density was maximum when Cu grain growth was facilitated. TB formation in nano-sized Cu grains was not controlled by grain size, but due to grain growth. The TB could be annealing twins caused by irregularities in the stacking sequence during relatively fast grain growth. The Cu film texture is concluded to be determined at the beginning of deposition, and the wettability of various barrier materials by the Cu films plays a key role in determining the film texture.     

Deformation-induced martensitic transformation behavior in cold-rolled and cold-drawn type 316 stainless steels

We investigate deformation-induced martensitic transformation behavior in cold-rolled and cold-drawn specimens of type 316 stainless steel. Deformation-induced martensite preferentially nucleates at the twin boundary between the austenite matrix and a deformation twin. In the cold-rolled specimen, martensite formed at the twin boundary has a Kurdjumov–Sachs (K–S) relationship with both the austenite matrix and the deformation twin (“double K–S relationship”). In the cold-drawn specimen, two kinds of deformation twins with different twin planes are typically formed, and therefore deformation-induced martensites are formed where the deformation twin boundaries intersect: martensite thus has an imperfect “triple K–S relationship” with the austenite matrix and the two deformation twins. The complicated crystallographic orientation relationship between austenite and martensite grains strongly restricts the formation of some variants of deformation-induced martensites. Because of the difference in number of nucleation sites in the cold-drawn and cold-rolled specimens, martensitic transformation is more enhanced in the former than in the latter.     

Porous Titania Ceramic Prepared by Mimicking Silicified Wood

A porous titania ceramic with a woodlike microstructure that was analogous to silicified wood was prepared. The production of "titanified wood" was performed using the following process: (i) introduction of titanium tetraisopropoxide into wood materials via vacuum infiltration, (ii) hydrolysis of the titanium tetraisopropoxide in the cell structure to form a titania gel, and (iii) firing at a temperature of 600°–1400°C in air. The resulting titania ceramic had the same external and internal forms of the original wood.     

Dynamic in situ observation of automotive catalysts for emission control using X-ray absorption fine structure

Two main pivotal subjects of research in automotive catalysts were studied by modern X-ray absorption analysis techniques. One is oxygen storage/release behaviour, and the other is sintering inhibition of Pt particles. First, three types of CeO₂–ZrO₂ (Ce:Zr = 1:1 molar ratio) compounds with different oxygen storage/release capacities and different structural properties were prepared, and the valence change of Ce as a function of temperature during oxygen release/storage processes was investigated. The reduction of surface Ce mainly occurred in the range 100–170 °C, and the reduction of bulk Ce progressed at high temperatures of 170 °C and above. The Ce reduction behaviour depended not only on the homogeneity of the Ce and Zr for bulk reduction at high temperatures but also on the particle size of the CeO₂–ZrO₂ samples for surface reduction at low temperatures. Secondly, sintering inhibition of Pt in Pt/Al₂O₃, Pt/MgO and Pt/ceria-based catalysts after 800 °C ageing in air was studied. We found that the Pt–O–M (M = Mg, Ce) bond acted as an anchor and inhibited the sintering of Pt particles on MgO or ceria-based oxide. Especially, it was noteworthy that the Pt–O–Ce⁴⁺ bond on the ceria-based support breaks easily through the reduction of Ce (Ce⁴⁺ → Ce³⁺) during the usual stoichiometric and reducing conditions.