Spin probe study of semi‐interpenetrating polymer networks based on polyurethane and polymethacrylate functional prepolymers

The motional transition and heterogeneity of semi‐interpenetrating networks (SIPNs) based on polyurethane (PU) with carboxylic groups and methacrylic copolymer (PM) with tertiary amine groups were studied by the electron spin resonance (ESR) spin probe method. The concentration of functional groups in both prepolymers varied from 0 to 0.45 mmol g^?1. Spin‐probed SIPNs show that the temperature‐dependent spectra are sensitive to polymer interactions imposed by functional groups. These interactions determine the free volume distribution in the matrix and temperature at which motional transition takes place. The fraction of free volume increases with functional group concentration and reaches its maximum at 0.25 mmol g^?1. Further increases in the functional group concentration reduce the free volume. The results of the networks with strong interactions are discussed in terms of the interference of the plasticizing effect of the PU component and the formation of possible cluster cross‐links, which restricts segmental motions. Copyright © 2003 Society of Chemical Industry     

Influence of accelerated ageing on methacrylate‐based denture resins heterogeneity as viewed by ESR‐spin‐probe method

The electron‐spin‐resonance (ESR) spin‐probe method, was used to study the heterogeneity of denture resins based on poly(methyl methacrylate). Results for three resins processed by microwave energy, conventional curing and cold curing (depending on the curing procedure and exposed to ageing in various environmental conditions) were compared. All three cured resins were stored over the same time (1200 h) in distilled water at ambient temperature and in artificial saliva at 348 K. The temperature‐dependent ESR spectra of a spin probe dispersed in the denture resins are analyzed in terms of line‐shapes and line‐widths. The appearance of two spectral components was taken as an indication of resin heterogeneity. The results reveal that the cold‐cured resin has a lower local density in comparison with microwave and conventionally cured resin. The amount of residual monomer also contributes to the local motion of polymer segments. The change of denture resins exposed to ageing is influenced both by the structure of the original resin and the ageing conditions. Restricted motion of a spin probe incorporated into the acrylic resins exposed to accelerated ageing suggests additional crosslinking of polymer chains. The differences are observed for all the investigated resins, but the highest change is observed with the cold‐cured resin. The ESR results are accompanied by T_g and T_m measurements. Copyright © 2005 Society of Chemical Industry     

A portable cryo-storage system for low-temperature scanning electron microscopy,suitable for international transport of cryo-specimens

A cryo-specimen storage system for low-temperature scanning electron microscopy (LTSEM) specimens is described, which: liberates multi-specimen experiments from sampling restrictions imposed by the rate at which LTSEM specimens can be examined in the SEM; provides security against experiment loss resulting from breakdown of the SEM or cryo-system; enables collection of specimens in the field or in laboratories remote from the SEM laboratory; and facilitates international air transport of LTSEM specimens. The components of the system, which has a capacity of 98 stub-mounted specimens, are readily made in a laboratory workshop. The details of the design may be altered to suit particular specimen types or experimental approaches.     

The As-prepared surfaces of C-axis-oriented Nd1Ba2Cu3Oy thin films characterized using scanning probe microscopes

Recently, superconducting Nd₁Ba₂Cu₃O_y (Ndl23) thin films with high superconducting transition temperature (T _c) have been successfully fabricated at our institute employing the standard laser ablation method. In this paper, we report the results of surface characterization of the Nd123 thin films using an ultrahigh vacuum scanning tunneling microscope/spectroscopy (UHV-STM/STS) and an atomic force microscope (AFM) system operated in air. Clear spiral pattern is observed on the surfaces of Nd123 thin films by STM and AFM, suggesting that films are formed by two-dimensional island growth mode. Contour plots of the spirals show that the step heights of the spirals are not always the integer or half-integer number of thec-axis parameter of the structure. This implies that the surface natural termination layer of the films may not be unique. This result is supported byI-V STS measurements. The surface morphology of the Nd123 thin films is compared with that of thec-axis-oriented Y₁Ba₂Cu₃S_y thin films. Surface atomic images of the as-prepared Nd123 thin films are obtained employing both STM and AFM. STS measurements show that most of the surfaces are semiconductive. The results of STS measurements together with the fact that we are able to see the surface atomic images using scanning probe microscopes suggest that exposure to air does not cause serious degradation to the as-prepared surfaces of Nd123 thin films.     

Laser scanning path generation considering photopolymer solidification in micro-stereolithography

It is essential to automate the scanning path generation process to effectively implement the micro-stereolithography. However, a scanning path that is generated based only on a 3D CAD model introduces dimensional inaccuracies. In micro-stereolithography, the photopolymer solidification is affected by fabrication conditions, such as the optical properties (laser power, laser scanning speed, laser scanning pitch focusing condition, etc.) and material properties of the photopolymer. Thus, the photopolymer solidification phenomena must be considered when generating a laser scanning path. In this paper, a scanning path generation algorithm that uses 3D CAD data and considers the photopolymer solidification phenomena is proposed to improve the dimensional accuracy in micro-stereolithography. Multi-line photopolymer solidification experiments were performed for various laser scanning conditions to examine the photopolymer solidification phenomena. From these experiments, linear relations between the solidification length (width) and scanning length (width) were acquired and stored in a database. Subsequently, these data were utilized to compensate the scanning path of the laser beam. In addition, experiments for determining the layer thickness in the z-direction were performed and these results were also used in the scanning path generation algorithm.This research was supported by the Highly Advanced National Project (http://www.most.go.kr), which performs some of the National R&D Program, and sponsored by the Korean Ministry of Science and Technology under the contract project code M10214000116-02B1500-02010.     

An Investigation of Milk Powders Produced by a Laboratory-Scale Spray Dryer

A mini spray dryer has been used to investigate morphological changes that occur to milk particles during the spray drying process. We have found that the mini spray dryer is ideal for such investigations, because phenomena such as skin and vacuole formation in particles can be analyzed without the added complication of particle agglomeration, which only occurs in much larger spray dryers where particle number concentrations are higher. We have confirmed observations made by various researchers that the bulk density of spray-dried milk powder is greatly affected by the drying temperature, due to the strong influence of the latter on the porosity of the particles. In addition, we have attempted to explain observations made by various workers that fat accumulates preferentially at the surface of a particle during drying by postulating that fluid fat is transported towards the surface, via a network of cracks and pores, by the development of a vacuole overpressure which is also responsible for the inflation of the particle. Finally, we have shown that milk powders can be spray dried a second time, by reconstitution with water, with no change to the thermodynamic characteristics of the resultant powder. Thus, milk concentrates for spray drying research can be prepared from already-spray-dried milk powders rather than using the more arduous evaporation method to concentrate unprocessed milk.     

Scanning electron microscope electron detector with a radial type discrete dynode electron multiplier

A discrete dynode electron multiplier with radial flux of electrons was built and tested in the range of low‐voltage scanning electron microscopy as a backscattered electron detector of topographic contrast. The multiplier collects backscattered electron emitted in a specific range of take‐off angles and over the whole azimuth angular range enabling large solid collection angle. Multipliers with different dynode shapes were studied theoretically with the use of the software for particle optics and three assemblies were built and tested experimentally. The gain estimation, assessment of the type of detected electrons (secondary electron or backscattered electron), imaging the spatial collection efficiency and signal‐to‐noise measurements were performed.     

钨系延期药预点火反应机理研究

通过程控升温模拟点火条件，根据ＤＳＣ图谱分析，找出主要反应区的温度范围。研究结果表明，钨系延期药预点火反应是一个真正的固－固反应。     

Early detection of ageing in solder joints through laser probe thermal analysis of the peltier effect

We have recently developed an optical contactless method for testing the quality of solder joints during accelerated thermal cycling ageing processes.¹ The method was based upon the measurement of the dynamic thermal behaviour of the joint to short bursts of Joule heating. It has proved to be efficient in revealing the formation of cracks at the lead-solder interface. We present a method to evaluate ageing at a much earlier stage in the cycling process. We have observed in earlier work,¹ that before cracks appear, structural changes occur in the solder at the lead-solder interface. The thermal response of the solder joint is recorded over time to a Peltier heat perturbation produced by flowing a current pulse through the interface where structural changes occur. The key point in this method is to discriminate the Peltier effect from the Joule thermal response because both effects generate heat. The variation of the early Peltier response in the thermal cycling ageing tests is seen as a quantitative signature of the structural changes in the lead-solder interface.     

Melting and crystallization behaviour of elastoplastic semicrystalline copolymers: poly(ether ester)

The melting and crystallization behaviour of an elastoplastic semi-crystalline poly(etherester) has been studied by differential scanning calorimetry. The shape of the melting endotherm is strongly dependent on heating rate and annealing time and results from the sum of simultaneous melting and crystallization phenomena. Samples prepared by different techniques, i.e. by solvent evaporation or by melt extrusion, behave very differently owing to specific crystal morphologies. By applying the Hoffman-Weeks plot, the equilibrium melting temperature has been extrapolated. The Avrami treatment allows the calculation of the index n and of the rate constant K from the isothermal kinetic data.