Poly(L‐lactide). X. Enhanced surface hydrophilicity and chain‐scission mechanisms of poly(L‐lactide) film in enzymatic,alkaline, and phosphate‐buffered solutions

Attempts were carried out to enhance the surface hydrophilicity of poly(L ‐lactide), that is, poly(L ‐lactic acid) (PLLA) film, utilizing enzymatic, alkaline, and autocatalytic hydrolyses in a proteinase K/Tris–HCL buffered solution system (37°C), in a 0.01N NaOH solution (37°C), and in a phosphate‐buffered solution (100°C), respectively. Moreover, its chain‐scission mechanisms in these different media were studied. The advancing contact‐angle (θ_a) value of the amorphous‐made PLLA film decreased monotonically with the hydrolysis time from 100° to 75° and 80° without a significant molecular weight decrease, when enzymatic and alkaline hydrolyses were continued for 60 min and 8 h, respectively. In contrast, a negligible change in the θ_a value was observed for the PLLA films even after the autocatalytic hydrolysis was continured for 16 h, when their bulk M_n decreased from 1.2 × 10⁵ to 2.2 × 10⁴ g mol^?1 or the number of hydrophilic terminal groups per unit weight increased from 1.7 × 10^?5 to 9.1 × 10^?5 mol g^?1. These findings, together with the result of gravimetry, revealed that the enzymatic and alkaline hydrolyses are powerful enough to enhance the practical surface hydrophilicity of the PLLA films because of their surface‐erosion mechanisms and that its practical surface hydrophilicity is controllable by varying the hydrolysis time. Moreover, autocatalytic hydrolysis is inappropriate to enhance the surface hydrophilicity, because of its bulk‐erosion mechanism. Alkaline hydrolysis is the best to enhance the hydrophilicity of the PLLA films without hydrolysis of the film cores, while the enzymatic hydrolysis is appropriate and inappropriate to enhance the surface hydrophilicity of bulky and thin PLLA materials, respectively, because a significant weight loss occurs before saturation of θ_a value. The changes in the weight loss and θ_a values during hydrolysis showed that exo chain scission as well as endo chain scission occurs in the presence of proteinase K, while in the alkaline and phosphate‐buffered solutions, hydrolysis proceeds via endo chain scission. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1628–1633, 2003     

Predicting nitrogen leaching with the modified LEACHM model: validation in soils receiving long-term application of animal manure composts

A variety of process-based models have been developed for predicting nitrogen (N) dynamics in agro-ecosystem; however, no reliable models have been validated for N leaching from soils receiving a long-term application of different types of animal manure composts. The Leaching Estimation and Chemistry Model (LEACHM) was recently modified by incorporating the basic structure of Rothamsted Carbon Model for extending its ability to describe soil organic matter decomposition and subsequent N leaching in soils rich in organic matter. We evaluate the applicability of the modified LEACHM in cropped Yellow soils receiving 10-year application of cattle or swine manure compost in addition to chemical fertilizers, where high-frequency field monitoring data of soil water contents, soil N contents and leachate N concentrations were available for the last 3 years. Particular attention was paid to determine all input parameters from independent measurements, parameterization from known soil properties or databases without optimisation to fit the measured field data. The model reasonably predicted temporal changes in the soil NH₄-N and NO₃-N contents, and inorganic N concentrations in the leachate as well as their differences due to different manure compost/chemical fertilizer applications. The simulations of leached N concentration yielded a Willmott index of agreement (IA) of 0.62–0.68, with those for soil moisture, soil nitrate content and crop N uptake all within an acceptable IA range. In view of the good performance without site-specific calibrations, the modified LEACHM appears to be a valuable tool for predicting N leaching from cropped soils receiving long-term manure compost applications.     

Phase Relations and Volume Changes of Hafnia under High Pressure and High Temperature

Using multi-anvil high-pressure devices and synchrotron radiation, X-ray in situ observations of HfO₂ under high pressure and high temperature have been performed to investigate its phase relations and compression behavior. An orthorhombic phase (orthoI) is stable from 4 to 14.5 GPa below 1250°–1400°C and transforms to a tetragonal phase, which is one of the high-temperature forms of HfO₂, above these temperatures. Another orthorhombic phase (orthoII) with a cotunnite-type structure appears above 14.5 GPa. OrthoII is stable up to 1800°C at 21 GPa. OrthoII is quenchable to ambient conditions. The orthoI-to-orthoII transition is accompanied by ∼8 vol% decrease. The bulk moduli of orthoI and orthoII at room temperature are 220 and 312 GPa, respectively. This low compressibility of orthoII indicates that it is a potential candidate for very hard materials.     

Dehydrogenative polycondensation of telechelically bis(dimethylsilyl)functionalized oligo(dimethylsiloxane)s or aromatics and 1,3,3,5,5,7,7,7-octamethyltetrasiloxane

Telechelically bis(hydrodimethylsilyl)-functionalized oligo(dimethylsiloxane)s or aromatics were found to give polymers constituting of alternating disilylene and oligodimethylsiloxane or 4,4′-diylaromatics as repeating units by dehydrogenative coupling reaction in the presence of palladium dibenzylideneacetone complex. The same catalyst gave polysilylenes with trisiloxane pendant from 1,1-dihydro-1,3,3,5,5,7,7,7-octamethyltetrasiloxane. Received: 18 October 1996/Accepted: 31 October 1996     

The α–β Transformation in Silicon Nitride Single Crystals

Single crystals of α-Si₃N₄ were annealed at 2000°–2150°C. The β phase was detected after annealing at 2150°C only when the crystals were surrounded by MgO·3Al₂O₃ or Y₂O₃ powders. On the other hand, no evidence of the α–β transformation was found when the crystals were annealed without additives. The solution–precipitation mechanism was concluded to be the dominant factor in the α–β transformation of Si₃N₄.     

Fabrication and Mechanical Properties of Continuously Graded MoSi2–ZrO2(2Y) Materials Using Wet-Molding

Continuously graded MoSi₂-ZrO₂(2Y) materials with high density (97.5% of theoretical) have been fabricated by uniaxial wet-molding, followed by hot pressing (1000°C/1 h/30 MPa) and hot isostatic pressing (1400°C/2 h/196 MPa). Their composition profiles are greatly influenced by the viscosity of mixed solutions of glycerin and ethanol used as a dispersion medium; a linear compositional gradient from MoSi₂/ZrO₂(2Y) 70/30 to 20/80 mol% is obtained from the solution (50/50 vol%) with a viscosity of 20 mPa s. Vickers hardness (Hv) and fracture toughness (KIC) increase from 9.7 to 12.4 GPa and from 5.1 to 12.5 MPa m1/2, respectively, with increasing ZrO₂(2Y) composition.     

Replication of Microstructures by Roll-to-Roll UV-Curing Embossing

The characteristics of pattern replication and releasing in a roll-to-roll ultraviolet- (UV) curing embossing process were investigated. The roll embossing system was designed for large-area continuous embossing, with employment of a fast curing resin, a heat damage protector, and a surface energy reducing coating. A 60° V-groove pattern with a groove period of 30 µm was embossed. It was found that the replication quality was profoundly influenced by the pattern geometry, the pattern direction, and the mold surface energy. In particular, the pattern direction significantly affected the edge sharpness and the surface topography of replicated features. In the parallel groove mode, a significant amount of tearing and sliding occurred, whereas in the transverse groove mode, biting marks were observed on the side wall of the V-groove. A simple mechanical model was used to explain the difference in pattern releasing with different pattern layouts. The replication quality was found to be significantly improved with the application of a fluorinated coating on the roll mold.     

THE EXTRACTION OF NEPTUNIUM(V) BY METHYLTRIOCTYLAMMONIUM CHLORIDE AND 1-PHENYL-3-METHYL-4-BENZOYL-5-PYRAZOLONE

The synergistic effect of methyltrioctylammonium chloride (QCI) on the extraction of Np(V) by 1-phenyl-3-methyl-4-benzoyl-pyrazolone(HP) in benzene is studied over the pH range 2-6. This system extracts Np(V) better than any previously reported. The interaction of the extractants and monomer-dimer equilibria affect the distribution behavior of Np(V) in a complicated manner. Analysis of the results suggests that NpO₂ ⁺ (M⁺) is extracted as mixed dimers, (QMP₂QCl)_o and (QMP₂QP)_o.     

Role of adsorbed iodine into poly(vinyl alcohol) films drawn in KI/I2 solution

We have investigated the microstructure of the poly(vinyl alcohol) (PVA) films using small- and wide-angle X-ray scattering (SAXS and WAXS, respectively) techniques. The samples were uniaxially drawn in water or KI/I₂ aqueous solution and then dried in an air-oven at 333 K for 1 h prior to SAXS and WAXS measurements. It was found that for the films drawn in KI/I₂ solution PVA chains in the microfibrillar structure are more extended upon the film drawing compared to the case of the films drawn in pure water, which is resulted from the correlation function analysis on the SAXS data. Adsorbed iodines into the film were anticipated to act as junction points between the microfibrils via the formation of the PVA-iodine complexes.     

Radiation detector made of a high-quality polycrystalline diamond

Radiation detector was made of a high-quality CVD polycrystalline diamond composed of frost column like structure diamond grains, and induced charge distribution spectra and drift velocities were measured by using alpha particles. As a result, the CVD polycrystalline achieved maximum induced charge of 83% of HP/HT type IIa diamond. Moreover, the CVD crystal had lower charge loss on electrons compared with the HP/HT type IIa diamond. Drift velocities of electrons and holes were v_e = 7.7 × 10⁴ and v_h = 7.3 × 10⁴cm/s at an electric field of 20 kV/cm, respectively. In addition, response function measurement for 14 MeV neutrons was carried out.