Hydrolytic degradation of poly(L-lactic acid): Combined effects of UV treatment and crystallization

Amorphous and crystallized poly(L -lactic acid) (PLLA) films were prepared and the hydrolytic degradation of the ultraviolet (UV)-treated and UV-nontreated films was investigated. This study reveals that the combination of UV and thermal treatments can produce the PLLA materials having different hydrolytic degradation profiles and that the UV-irradiation in the environment will affect the design of recycling process for PLLA articles. In an early stage, the degrees of hydrolytic degradation monitored by weight loss (W_loss), number-average molecular weight (M _n), and melting temperature (T _m) were higher for the UV-treated films than for the UV-nontreated films. In a late stage, the trend traced by W_loss was reversed, and the difference in the degrees of hydrolytic degradation between the UV-treated and UV-nontreated films monitored by M _n and T _m became smaller, with the exception of the degrees of hydrolytic degradation of the amorphous films traced by T _m. Also, in the early stage, the degrees of hydrolytic degradation monitored by W_loss and M _n were higher for the crystallized films than for the amorphous films. In the late stage, this trend was reversed, with the exception of the degrees of hydrolytic degradation of the UV-treated films monitored by M _n. The main factors that determined the W_loss and T _m were the molecular weight and initial crystallinty but not the molecular structures such as terminal CC double bonds and crosslinks. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Group behavior of agents with an emotional model

Recently, there has been much interest in the study of the formation of groups of agents that cause interactions between agents and invent new functions. We gave some agents an action rule based on the interactions of human feelings by using a circumplex model. It had been decided that the parameters of feelings in this model should have only two axes. In this report, eight basic action dimensions and pure feelings on four corresponding axes were given to agents as a model of feelings and actions based on the multiple factor analysis theory of R. Plutchik, and the behavioral characteristics of the group of agents were examined.     

Porous biodegradable polyester blends of poly(L‐lactic acid) and poly(ε‐caprolactone): physical properties,morphology, and biodegradation

Poly(L ‐lactic acid) (PLLA), poly(ε‐caprolactone) (PCL), and their films without or blended with 50 wt% poly(ethylene glycol) (PEG) were prepared by solution casting. Porous films were obtained by water‐extraction of PEG from solution‐cast phase‐separated PLLA‐blend‐PCL‐blend‐PEG films. The effects of PLLA/PCL ratio on the morphology of the porous films and the effects of PLLA/PCL ratio and pores on the physical properties and biodegradability of the films were investigated. The pore size of the blend films decreased with increasing PLLA/PCL ratio. Polymer blending and pore formation gave biodegradable PLLA‐blend‐PCL materials with a wide variety of tensile properties with Young's modulus in the range of 0.07–1.4 GPa and elongation at break in the range 3–380%. Pore formation markedly increased the PLLA crystallinity of porous films, except for low PLLA/PCL ratio. Polymer blending as well as pore formation enhanced the enzymatic degradation of biodegradable polyester blends. Copyright © 2006 Society of Chemical Industry     

Real‐time spectral analysis

For signal analysis, the Fourier transform and the linear prediction methods are the main approaches. In recent years, the wavelet transform, which gives an expression in the time–frequency domain, has been attracting attention. In the wavelet transform, scale and shift operations are used to analyze regional waves in the signal. In this paper, we propose a new method for signal analysis. Instead of the wavelet, short sine waves and cosine waves which have slightly different frequencies and phases established beforehand are used. These frequencies and phases play the same role as wavelets in analyzing regional waves in the signal. However, our proposed method is different from the wavelet transform because it does not use multiresolution analysis. In conventional spectral analysis methods, all data are prepared beforehand and calculations are performed by using these data. In the proposed method, the spectrum is updated whenever new signal data come in. We show that the amount of calculation is markedly reduced and that real‐time spectral analysis can be achieved. Finally, we present an analysis of Japanese vocal sounds using the proposed method. © 2007 Wiley Periodicals, Inc. Electr Eng Jpn, 161(1): 43–50, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.20504     

Water Vapor Permeability of Poly(L‐lactide)/Poly(D‐lactide) Stereocomplexes

PLLA/PDLA blend films with only stereocomplex crystallites as a crystalline species together with pure PLLA and PDLA films with only homo‐crystallites as a crystalline species were prepared, and the effects of enantiomeric polymer blending, crystalline species, and crystallinity on the water vapor permeability were investigated. The WVT coefficient P of PLLA/PDLA blend films was 14–23% lower than that of pure PLLA and PDLA films in the crystallinity X_c range of 0–30%. Amorphous PLLA/PDLA blend films have a much lower P than pure PLLA and PDLA films. The dependence of P on X_c for blend films was stronger for X_c = 0–30% than for X_c = 30–100%. This dependence is discussed using the Nielsen model and the concept of “restricted” (or “restrained”) and “free” amorphous regions.

     

Classification of particles by centrifugal separator and analysis of the fluid behavior

This study gives fundamental knowledge on the particle classification performance by centrifugal separator.It is found that the cut size of a centrifugal separator decreases as the rotational speed increases and the liquid flow rate decreases. Fitting our experimental results with the theory, they agree with each other at high flow rate. However, the difference between them generates at low flow rate. This is because dead spaces are generated in the centrifugal separator at the low flow rate. Also, the computer simulation of the fluid behavior in the centrifugal separator can find the decrease of the velocity near the wall under the low flow rate, which suggests the possibility of the formation of dead spaces in the separator.     

Preparation of cured epoxy resin particles having one hollow by polyaddition reaction

In 1996, the authors proposed a novel method to prepare micron-sized, hollow cross-linked polymer particles. This method is based on the self-assembling of phase separated polymer at interface with water, which was named SaPSeP method, formed by suspension polymerization of divinyl monomer in toluene droplet dissolving previously polystyrene. The SaPSeP method was developed to be applicable to polyaddition reaction system of epoxy resin with diamine. The presence of PS dissolving in epoxy/diamine/toluene droplets promotes the phase separation of the epoxy resin reacted with the diamine. The epoxy resin molecules tend to adsorb at the interface of the droplets. These points were accord with the required conditions for the preparation of hollow particle by the SaPSeP method. Cured epoxy resin particles having one hollow were successfully prepared by the polyaddition reaction in the dispersed system of Epikote 806/630/604, of which equivalent ratio was 5/4/1.     

Study of point defects in CuGaSe2 single crystals by means of electron paramagnetic resonance and photoluminescence

Point defects in CuGaSe₂ single crystals as vacancies V_Se, V_Cu and defect pair (2V_Cu⁻+Ga_Cu²⁺) have been studied by means of electron paramagnetic resonance (EPR) and low-temperature photoluminescence (PL). EPR hyperfine structure has been found at temperatures as low as 1.45–45 K and the temperature dependence of EPR line is discussed. Photo-EPR spectrum reveals optically active behavior of intrinsic point defects in CuGaSe₂ crystals. Three bands of PL emission show different origins and two low-energy bands at 1.55 and 1.58 eV have been found to be steady despite H₂-, O₂- and Se₂-annealings. The experimental data added with electric characterization in accordance with the used annealings and together with a defect physics model allow consideration of the point defect ensemble in CuGaSe₂ in more detail.     

Heat Transfer & Thermal Stress Analysis of Plastic-Encapsulated ICs

Analytic approaches of thermal stress in plastic-encapslated ICs reliability have been studied using a simple, 2-dimensional model of the cross section of ICs by the finite-element method. To test the validity of the model, the actual stress within the silicon chip was measured using piezoresistive devices. The calculated stress in the silicon chip agreed with the experimental values. The stress distributions were changed by lead-frame properties. Package cracking, and delamination between the molding plastic and the lead-frame were qualitatively explained. We estimated the effect of the plastic properties on stress quantitatively. Furthermore, to test the validity of this model, the temperature change at the silicon chip was measured using the Vf temperature dependency of a diode. The calculated temperature change at the silicon chip agreed with the observed values. A very high temperature gradient was observed near the surface of the plastic immediately after solder dipping. The non-uniform temperature distributions produced different thermal stress distributions than those observed in the steady-state. This result indicated that rapid thermal shock could delaminate the plastic from the lead-frame. We believe that these results can guide the development of an optimum low-stress plastic.     

Surface hydrophilicity and enzymatic hydrolyzability of biodegradable polyesters: 1. effects of alkaline treatment

Surface treatment using alkaline solutions was attempted to enhance the surface hydrophilicity and enzymatic hydrolyzability of hydrophobic poly(L ‐lactide) [ie poly(L ‐lactic acid) (PLLA) and poly(ε‐caprolactone) (PCL). The alkaline treatment was performed by immersing the PLLA and PCL films in 0.01 and 4 N NaOH solutions, respectively, for various periods of time. The effects of the alkaline treatment on the hydrophilicity of the films were monitored by dynamic contact angle measurements, while the enzymatic hydrolyzability of the PLLA and PCL films after the alkaline treatment were evaluated by weight losses in the presence of proteinase K and Rhizopus arrhizus lipase, respectively. With the alkaline treatment the hydrophilicity of the PLLA and PCL films was controllable in the advancing contact angle (θ_a) ranges of 84–108° and of 69–93°, respectively, by varying the alkaline treatment time. The enzymatic hydrolysis rates of the PLLA films became higher with decrease of the θ_a, irrespective of the crystallinity, strongly suggesting that the surface hydrophilicity or the surface molecular weight is crucial to determine their enzymatic hydrolyzability. In contrast, the enzymatic hydrolyzability of the PCL films remained unchanged even when the θ_a decreased from 93° to 73° by alkaline treatment for 4 h. However, prolonged alkaline treatment for periods of time exceeding 4 h, which insignificantly altered the θ_a but caused the formation of pores and cracks on the PCL film surface, accelerated the enzymatic hydrolysis of the PCL films. This indicates that the enzymatic hydrolyzability of the PCL film depends on the surface area per unit weight rather than the surface hydrophilicity. Copyright © 2003 Society of Chemical Industry