Depolymerization of fluoroalkyl methacrylate polymers as studied with thermogravimetry

Thermal behaviors of a few kinds of poly(fluoroalkyl methacrylate) prepared by γ-or UV-ray polymerization were investigated by using thermogravimetric measurements with the intermittent analysis of the gaseous products. The degradation of fluoroalkyl methacrylate polymers, monomeric units of which were CH₂=C(CH₃)COOCH₂(CF₂CF₂)_nH, n = 1, 2, and 3, proceeded according to the depolymerization mechanism reproducing the pristine monomer exclusively, but the thermogram in inert atmosphere showed the features of a two-step reaction. Two species of polymer differing in the heat stability were supposed to exist in the polymeric substance produced by γ- or UV-ray irradiation, and the fraction of polymer having lower heat stability increased with the increasing length of the fluoroalkyl ester group. In air, however, the thermogram of poly(fluoroalkyl methacrylate) showed no such a stepwise weight decrease as was observed in inert atomsphere with the elevating temperature, and the temperatures at which the depolymerization was introduced shifted to a much higher region. The results were ascribed to the reaction of initiating polymer radicals produced on polymer having lower stability with oxygen to form hydroperoxide, which once stabilized the polymer radicals and obstructed the initiaition of the unzipping reaction till higher temperature.     

Depolymerization of poly(fluoroalkyl methacrylate-co-methyl methacrylate) as studied with thermogravimetry

Thermal behaviors of a few kinds of poly(fluoroalkyl methacrylate-co-methyl methacrylate) prepared by γ-ray copolymerization were investigated by using thermogravimetric measurements together with the intermittent analysis of the gaseous products. The thermal degradation of copolymers composed of one of fluoroalkyl methacrylates of the following structures: CH₂?C(CH₃)COOCH₂(CF₂CF₂)_nH, where n = 1,2, and 3, and methyl methacrylate proceeded according to the depolymerization mechanism reproducing the pristine component comonomers exclusively, but their thermograms in inert atmosphere showed the feature of a two-step reaction. In air, however, thermograms of copolymers did not show such a stepwise decrease in weight with the elevating temperature, and temperatures at which depolymerization was introduced shifted to a much higher region. The overall aspects of depolymerization of copolymers seemed to be much similar to that of fluoroalkyl methacrylate homopolymer previously reported, and the retardation of depolymerization by air was considered to be due mainly to the stabilization of once-formed polymer radicals by oxygen.     

A record-linkage study on risk factors for cause-specific infant mortality

Infant death certificates were linked with birth certificates for infants born to residents of Tohoku, Tokai and Kyushu regions in 1989 (n = 409, 679, or about one-third of all births in Japan), to examine the effects of variables, as reported on birth certificates, on cause-specific infant mortality. "Certain conditions originating in the perinatal period" and "congenital anomalies" accounted for nearly 90 percent of neonatal deaths, while "congenital anomalies", "injuries and poisoning" and "sudden infant death" were responsible for about 65 percent of postneonatal deaths. Mortality rates for almost all causes of infant deaths, except injuries and poisonings, increased as birth weight decreased not only in the neonatal period but also in the postneonatal period. This suggests that low birth weight places some infants at higher risk of death, and conditions that lead to low birth weight independently contribute to the risk of infant death. Cox's proportional hazards linear model was used to assess the effects of variables on infant mortalities by causes of death. An extremely strong birth weight effect was noted for "certain conditions originating in the perinatal period" and "congenital anomalies". Being a male infant and late order of birth in multiparity were other risk factors for deaths from "congenital anomalies", while being a male infant, resident of Tohoku region and maternal stillbirth experience related to deaths from "certain conditions originating in the perinatal period". Elevated risks of sudden infant death syndrome (SIDS), of which mortality rate in Japan was considerably lower than those in most developed Western countries, i.e. 0.23 per 1,000 live births in 1989, were associated with low birth weight, being a male infant, low maternal age, late order of birth in multiparity and illegitimacy. Low maternal age, late order of birth in multiparity and illegitimacy, also, related significantly to increased risk of infant deaths for "injuries and poisoning". These results suggest the independent contributions of socioeconomic factors to infant mortality, especially postneonatal mortality, from SIDS, "injuries and poisonings".     

Approximation of frequency responses based on Larsson's method

This paper discusses the new aspects of the formulation for structural model updates presented by Larsson and Sas at the 10th International Modal Analysis Conference held in San Diego, California in February 1991. First, a closed-form representation of the reduced impedance matrix is presented. It clarifies the issues associated with the range of the excitation frequencies used in model updates. Second, the applicable range of excitation frequencies is considered through an example where low frequency local modes are present. Third, the computational aspects of this algorithm are studied. It is shown that displacement sensitivity vectors corresponding to the virtual loads are critical in the computation of the reduced impedance matrix sensitivity. Finally, applicability of this algorithm for approximate frequency responses in structural optimization is studied. Numerical results are included to illustrate the essence of this formulation.[B1] Viscous damping matrix (N × N) - [B2] Structural damping matrix (N × N) - [E] Impedance matrix (N × N) [E] = [K+i(B ₁+B₂)–²M] - F Forcing vector used for analysis (N × 1) - G Measured force vector (N × 1) - [H] Receptance matrix (N × N) [H] = [E]^–1 - J Number of independent loading cases - [K] Stiffness matrix (N × N) - K Number of degrees of freedom where frequency responses are measured - KT Total number of responses for which measured data are available - L Number of excitation frequencies for each loading case - [M] Mass matrix (N × N) - M Number of parameters modified for system identification or design optimization - N Total number of structural system degrees of freedom in the analysis model - R Structural response - Q Number of vectors used in the modal analysis - U Frequency responses computed analytically - V Frequency responses measured in the shake tests - 0 Status prior to perturbation - model Quantities computed by an analysis model - red Indicates a reduced system obtained by isolating the measuredK degrees of freedom - test Quantities measured in the vibration tests - ~ Approximate quantity     

Building up the science of welfare care

An imposing amount of knowledge has been produced during the course of three hundred years of research in the field of occupational medicine and in other specialisations that in the last fifty years developed as branches of this discipline (industrial hygiene, industrial toxicology, respiratory physiopathology, etc). Part of this scientific heritage has been used to the full to plan and carry out prevention measures that have led to improved working conditions in many sectors of industry. Examples are the successes obtained in the prevention of pneumoconioses, aplastic anaemia and leukemia due to benzene, cancer caused by aromatic amines, and diseases occurring in pesticide users and consumers of agricultural products treated with such products. More recently, through original research programmes, with particular reference to the "Clinica del Lavoro" of Milan, a theoretical revision was made of the conception and method for analysing the relationship between organised work and health, resulting in an organic arrangement of the variables and procedures for the analysis of working conditions for the purposes of prevention. Other ways and areas where scientific bio-medical knowledge can be used are: a) planning of prevention measures on a vast social scale; b) variables and indicators for planning and assessing services designed for diagnosis and prevention of occupational risks and diseases; c) development of training programmes. In spite of these positive results, European Community statistics show that still too many occupational accidents and work-related diseases occur all over the world, especially in the developing countries, because the amount of scientific knowledge used is still much smaller than what is already available. The causes of this situation are many, among which those of a cultural nature. The author proposes the setting up of an "International Network for the History of Occupational and Environmental Prevention", and furnishes a detailed illustration of the aims and foreseeable initial actions.     

Characterization of microbial community structures and their activities in single anaerobic granules by beta imaging, microsensors and fluorescence in situ hybridization

The spatial distribution of microorganisms and their in situ activities in anaerobic granules were investigated by fluorescence in situ hybridization (FISH), beta imaging and microsensors. FISH results revealed a layered structure of microorganisms in the granule, where Chloroflexi was present in the outermost layer, Smithella spp. and Syntrophobacter spp. were found in a depth of ca. 100 μm, and Archaea was restricted to the inner layer (below ca. 300 μm from the surface). Substrate uptake patterns elucidated by beta imaging demonstrated that glucose uptake was highest at 50 μm depth, whereas propionate uptake had a peak at 200 μm depth. In addition, microsensor measurements revealed that acid was produced mainly at 100 μm depth and H(2) production was detected at a depth from 100 to 200 μm. H(2) consumption and corresponding CH(4) production were found below 200 μm from the surface. Direct comparison of these results implied sequential degradation of complex organic compounds in anaerobic granules; Chloroflexi contributed to fermentation of organic compounds and acid production in the outermost layer, volatile fatty acids were oxidized and H(2) was produced mainly by Smithella spp. and Syntrophobacter spp. at a depth from 100 to 200 μm, and Archaea produced CH(4) below ca. 300 μm from the surface.     

Comparison between SiO2 films deposited by atomic layer deposition with SiH2[N(CH3)2]2 and SiH[N(CH3)2]3 precursors

Thin SiO₂ layers were deposited by atomic layer deposition (ALD) using either Bis-dimethylamino-silane (BDMAS: SiH₂(N(CH₃)₂)₂) or Tris-dimethylamino-silane (TDMAS: SiH(N(CH₃)₂)₃) precursors. The purpose of this study is to evaluate these precursors for their suitability for ALD of hafnium (Hf)-silicate gate dielectrics. The advantages of these precursors are that the melting points and vapor pressures are moderate. The thickness of SiO₂ deposited using ALD process is controlled by the number of growth cycles and the growth rate was different for each precursor, that for BDMAS being 1.5 times that for TDMAS at the same reactor pressure. The carbon impurity in the SiO₂ film deposited using BDMAS was about half an order of magnitude less than that using for TDMAS. Furthermore, the carbon impurity was reduced to about the detection limit of secondary ion mass spectrometry after high temperature annealing at 1000 °C during 5 s.     

Kinetics of reactive diffusion between Au and Sn during annealing at solid-state temperatures

The reactive diffusion between Au and Sn was experimentally studied at solid-state temperatures using Sn/Au/Sn diffusion couples prepared by a diffusion bonding technique. The diffusion couples were annealed at temperatures of T = 393 and 473 K for various times in an oil bath with silicone oil. After annealing, compound layers composed of AuSn₄, AuSn₂ and AuSn were recognized to form at the Au/Sn interface. The thickness of the AuSn₄ layer is about six and four times greater than those of the AuSn₂ and AuSn layers at T = 393 and 473 K, respectively. The ratio of the thicknesses of the compound layers is kept constant independently of the annealing time. The total thickness l of the compound layers is described as a function of the annealing time t by the equation l = k(t/t₀)ⁿ, where t₀ is unit time, 1 s. The exponent n is nearly equal to 1/2 at T = 393 K but takes a value between 1/4 and 1/2 at T = 473 K. Such an intermediate value of n at T = 473 K indicates that the grain boundary diffusion contributes to the reactive diffusion and the grain growth occurs at certain rates. As the annealing temperature decreases, the contribution of the grain boundary diffusion should become more remarkable, but the grain growth will slow down. Consequently, n becomes close to 1/2 at T = 393 K. According to the constancy of the ratio of the thicknesses, it is concluded that the same rate-controlling process works in the AuSn₄, AuSn₂ and AuSn layers at a constant annealing temperature.     

Stabilization of a Power System Including Inverter‐Type Distributed Generators by a Virtual Synchronous Generator

The capacity of distributed generators (DGs) connected to the grid by inverters is growing year after year. The inverters are generally controlled by a phase locked loop (PLL) in order to achieve synchronization with the power system frequency. Power systems may become unstable as the capacity of the inverter‐type DGs continues to increase, because the inverter frequency is controlled just to follow the frequency determined by other synchronous generators. It has been suggested that inverters be controlled to behave like a synchronous generator. This concept is referred to as the virtual synchronous generator (VSG). In this paper, a control scheme for a VSG is presented, and the design method for the required energy storage and the capacity for grid stabilization control by a VSG is investigated by computer simulations.