Influence of silica fillers during the electron irradiation of DGEBA/TETA epoxy resins, part II: Study of the thermomechanical properties

This work describes the influence of silica fillers on the thermomechanical properties of diglycidyl ether of bisphenol A/triethylenetetramine (DGEBA/TETA) epoxy resins during ageing under electron beam irradiation. Whatever be the silica filler (pure micrometric ground and spherical silicas, nanometric silicas and coupling agent treated silicas), the glass transition temperature of the epoxy resins decreases with increasing irradiation dose, meaning that the main effect of the irradiation is chain scission. No influence of the silica fillers has been detected from the changes in the glass transition temperature with the increase in the irradiation dose. The disappearance of the cooperativity of the γ relaxation, the decrease of the α relaxation and the decrease of the elastic modulus at the rubbery plateau observed by dynamic mechanical analyses involve a decrease in the crosslink density of the epoxy resins. The occurrence of chemical reactions between the epoxy resin and the silica surface at high irradiation doses has been shown. Moreover, we show evidence that chemical reactions between the epoxy resin and the silica surface occur at high irradiation dose.     

Preparation and properties of macroreticular resins containing thiazole and thiazoline groups

Three macroreticular polystyrene-based resins with amino- or imino-thiazole and thiazoline groups as the functional groups have been prepared. The resins are highly stable in acid and alkaline solutions and have high selectivity for mercury(II). In the presence of hydrochloric acid, sorption of mercury attains equilibrium fairly rapidly, the time for 50% uptake of mercury being 3-6 min. There are practically no interferences. In a column operation, mercury is quantitatively recovered by elution with 0.1M hydrochloric acid containing 5% thiourea. The thiazoline resin column can be used to concentrate mercury from sea-water.     

Application of ftir spectroscopy to the study of curing of glass reinforced polyester composites

The effect of glass fiber reinforcements on the curing behavior of unsaturated polyester commercial resins was investigated by Fourier transform infrared spectroscopy. Two different E-glass fibers and two commercial resins were employed. The results indicate that both the glass fiber content and the fiber size have a pronounced effect on the ultimate values of the styrene conversion. Some complications found in the infrared analysis of commercial resins are also presented.     

Epoxy‐amine reticulates observed by infrared spectrometry. II. Modifications of structure and of hydration abilities after irradiation in a dry atmosphere

This article is part of a series of articles devoted to the study of the responsibilities of both humidity and irradiation in the aging process of amine‐cured epoxy resins. The basic technique used in this study is infrared spectrometry. In a previous article we have observed, with this technique, hydration of two kinds of epoxy resins, which are widely used in the nuclear industry. In this article the same technique is used to observe the same resins, which have been previously submitted to ionizing radiations. It allows us to determine the effects these radiations have on these resins at molecular level and how they consequently modify their hydration mechanisms. It could thus be established that irradiation by electrons almost does not induce modifications on resins cured with aromatic diamines, which results in their hydration capacity being only slightly changed. Irradiation by γ rays induces stronger modifications, which reflect themselves in a greater capacity of absorption of water and different ways of fixing H₂O molecules. Epoxy resins cured with alkyl diamines are more sensitive to irradiation and, after it, absorb a greater amount of H₂O molecules. After irradiation, steric conditions, which hinder H₂O molecules to bind on other H₂O molecules, apparently become less severe. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 329–340, 2000     

Influence of silica fillers during the electron irradiation of DGEBA/TETA epoxy resins, part III: Solid-state NMR investigations

The influence of silica fillers on chemical modifications of diglycidyl ether of bisphenol A/triethylene tetramine (DGEBA/TETA) epoxy resins induced by electron beam irradiation has been studied by ¹³C CP-MAS (Cross Polarisation and Magic Angle Spinning) NMR. Four kinds of silica filler were investigated: a pure micrometric silica, a treated micrometric silica, a pure nanometric silica and a treated nanometric silica. On the unirradiated epoxy resins, the magnetization transfer curves reveal structural differences due to the kind of silica fillers. A decrease of the epoxy network rigidity in the presence of nanometric silica fillers is shown. During irradiation, the formation of phenolic ends and enamine functions is confirmed. The slowing of the magnetization transfer of the pure and treated micrometric silica filled epoxy resin reveals an important decrease of the rigidity of these resins. On the pure and treated nanometric silica filled epoxy resins, reactions of the reactive species created by the irradiation in the epoxy resin and the silica particles surface are shown.     

Improved analysis of process liquors for the pulp and paper industry by ion chromatography

In this paper, techniques are presented to overcome interferences from caustic matrices and neighboring ions found in process solutions. Column switching and the use of low-capacity columns to characterize strongly retained analytes are described. Oxalate, sulfide, sulfite, sulfate and thiosulfate are characterized on one set of separator columns. High-capacity cation-exchange resins are shown to be an effective pre-treatment tool for neutralizing a caustic chlorine dioxide scrubbing liquor, enabling baseline resolution of chlorate.     

Effect of irradiation on AMP based resins for cesium separation from HNO3 feed solutions: batch and column studies

Three different resins containing ammonium molybdophosphate (AMP), viz. PMMA (polymethylmethacrylate) resin, composite AMP resin and ALIX (a bisphenol based resin), were evaluated for their irradiation stability. The studies included batch as well as column studies and were carried out for cesium uptake behaviour at 3 M acidity. The resin beads were irradiated to varying dose viz., 0 MRad, 10 MRad, 20 MRad, 50 MRad and 100 MRad. The time taken to attain equilibrium was rather long and about 2–5 h were found to be required for attaining equilibrium in batch studies. Batch Cs(I) uptake studies revealed no significant effect on the K _d values in case of the PMMA resin while in case of the composite resin and ALIX resin, a decrease in the K _d was observed as a function of irradiation dose. The resin capacity indicated contrasting behaviour with irradiation dose for the resins. Column runs have been carried out for the uptake of radio cesium using both unirradiated and irradiated resins using feed solutions containing 3 MHNO₃. The loading capacities of the resins were found to be proportional to their Cs loading capacities observed in batch studies. Study revealed that the composite AMP had the maximum and PMMA has the least loading capacity. Results of these studies show that these AMP based resins can be used for cesium separation from acidic nuclear waste.     

Epoxy–amine reticulates observed by infrared spectrometry. III. Modifications of the structure and hydration abilities after irradiation in a humid atmosphere

This article is the third part of a series devoted to the study of the responsibilities of both humidity and irradiation in the aging process of amine‐cured epoxy resins. The basic technique used in this study was infrared spectrometry. In previous articles, we described the hydration of two kinds of epoxy resins widely used in the nuclear industry. In the first article, we reported results concerning the hydration of unirradiated resins; in the second article, these resins were first submitted to ionizing radiation in a dry atmosphere. In this article, we describe the effects of irradiation in a humid atmosphere and compare these effects to what was observed after irradiation in a dry atmosphere, as described in the previous articles. These effects were subtle: the humidity of the ambient atmosphere apparently protected the resins from oxidative degradation because, after irradiation in a humid atmosphere, a smaller number of carboxylic groups were formed. However, the water uptake increased after irradiation in a humid atmosphere. Thus, the humidity of the ambient atmosphere at the same time favored the rupture of chains, which released steric hindrances and allowed a greater number of H₂O molecules to reach hydrophilic sites in the resin. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1129–1136, 2001     

Adsorption of surfactants onto acrylic ester resins with different pore size distribution

In this study, a series of acrylic ester resins with different pore size distribution were prepared successfully by varying the type and the amount of pore-forming agents. In order to inves-tigate the adsorption behavior and mechanism of surfactants on acrylic ester resins, three kinds of surfactants were utilized as adsorbates that were sodium 6-dodecyl benzenesulfonate (6-NaDBS), sodium 1-dodecyl benzene sulfonate (1-NaDBS) and sodium 1-dodecyl sulfonate, respectively. It was observed that the surface area was available in a particular pore size and an appropriate pore size of resins appeared to be more important for the adsorption of surfactants. As compared to commercial acrylic ester resins XAD-7 and HP2MG, 50# and 38# resins exhibited more excellent adsorption properties toward 1-NaDBS and 6-NaDBS. The experimental equilibrium data were fitted to the Langmuir, and double-Langmuir models. Two models provided very good fittings for all resins over the temperature range studied. The investigation indicated that electrostatic attraction and hydrogen bond between resins and surfactants were the main forces and had an obvious effect on adsorption proc-ess.     

Photosensitive resists used in microlithography

For the electronics industry, resists are resins that can be applied to a substrate in a pattern of exposed and covered areas to leave some areas open for later etching or plating while protecting others for many types of printed circuit boards, whose lines and spaces are 40 nm or more wide, screening is sufficient to give needed resolution. But integrated circuit chips need the finer resolution afforded by photolithography, which uses light sensitive resists for imaging. The new lithographic processes that integrated-circuit makers are looking at include those based on deep-ultra violet (less than 300 nm), electron beam, and x-ray irradiation. Until now, the near-UV region has been satisfactory, such as at the 436/404, and 366 nm lines of mercury sources. Photoresists may be either positive or negative. Negative photoresists include resins, such as cyclised polybutadiene or polyisoprene, mixed with a bis(azide), which become crosslinked and in-solubilized by exposure to ultraviolet light. UV irradiation photolyses bis-(azides) to bis(nitrenes), which form aziridine groups with double bonds of neighboring chains. Developing exposed negative photoresists in a solvent dissolves away resin from unexposed areas. Positive resists are formulations like phenolic resins mixed with relatively large amounts of light sensitive solubility inhibitors, such as diazonaphtoquinones. On exposure to light, the solubility inhibitors rearrange to acidic compounds that can be leached out by bases. Thus, exposed areas of positive resists are the ones dissolved away on development. Alternatively, positive resists can be resins that are depolymerized by irradiation.     

Novel UV-curable and alkali-soluble resins for light-shielding black matrix application

A carbon black (CB) photo resist, comprising CB, CB dispersant, photo-curable resin, photo-initiator, and solvent, has been developed in order to prepare a light-shielding black matrix (BM) in the liquid crystal display application. In order to prepare a BM with a high opacity property or optical density (OD), the effect of CB such as its particle and concentration on light absorption property was first evaluated, and the results showed that 45 wt% CB with a particle size of about 100 nm in BM could reach an OD value of 4 μm⁻¹. Moreover, six different UV-curable and alkali-soluble resins (A1, A2, and A3; B1, B2, and B3) were synthesized as photo-curable resins. Structures of these resins were characterized by FTIR and GPC, in which concentrations of various functional groups, especially carboxylic acid and double bond, were calculated. Subsequently, their photo-initiated polymerization rate with or without CB were measured. Finally, it was found that through a proper selection of the newly synthesized resins to prepare a carbon black photo resist, a BM with an OD of 4 μm⁻¹ and a good resolution of 10 μm was successfully prepared upon low UV irradiation energy of 50 mJ/cm².     

Radiation resistance of pyridine type anion exchange resins for spent fuel treatment

The resistance against radiation of the tertiary pyridine resins synthesized for the treatment of spent nuclear fuels and high level radioactive waste was evaluated. After irradiation at 10 MGy, only approximately 10% or less of the exchange groups were lost in HCl solutions regardless of their concentrations, while 3040% were lost in HNO₃. The pyridine resin has shown remarkable resistance against radiation particularly in HCl solution. It has been revealed that the decomposition of pyridine type resins results from the scission of the principal chains. An irradiation study was conducted also on the quaternary ammonium resins. Quatemization ratio was found to be reduced in HNO₃ solutions at 10 MGy irradiation.     

商用聚丙烯酸类高吸水树脂粒子尺寸及分布与其凝胶浓度的关系

研究了6种商用聚丙烯酸类高吸水树脂(SAP)粒子尺寸大小及分布对其形成凝胶的临界浓度的影响,通过傅里叶变换红外光谱、X射线光电子能谱对样品的成分进行了分析,使用光学显微镜和ImageJ软件统计了样品未吸水时粒子的尺寸及分布,通过测定样品吸水后的膨胀比,估算得到了样品吸水后的粒子的尺寸及分布,用流变学方法和倒置实验法测定了高吸水树脂形成凝胶的临界浓度(凝胶点)。 结果表明,这6种商用聚丙烯酸类高吸水树脂吸水后的粒子的尺寸大小对其形成凝胶的临界浓度的影响不符合理论预测,这是由于粒子尺寸分布宽度不均一造成的。 在选择粒子大小分布占优的均一范围内,样品的凝胶浓度随着粒子尺寸的增大而降低。     

P507萃取分离-二甲酚橙光度法测定锆铪

本文用自合成的P507萃淋树脂对锆铪吸附特性进行研究,并对此树脂的离子交换柱性能进行了研究与测定;在此基础上,对不同配比锆铪混合液进行分离,作出了分离曲线,并采用二甲酚橙分光光度法对锆铪进行了测定.研究了干扰离子存在的允许量及树脂的使用寿命.     

Contribution a l’etude de la determination de Be,B, C,N, O et F par activation Au moyen de p,d,3He et α

A set of curves and numerical values is given, representing the relative importance of the main nuclear interferences involved in the determination of Be, B, C, N, O and F by p, d,³He and α activation. The possibilities offered by these charged particles and γ photons are compared, taking into account detection sensitivities on the one hand and interferences on the other. It is then possible to define the optimum irradiation conditions for the standard determination of each of these light elements.     

Observations relative to epithermal and fast neutrons in INAA

Various theoretical and practical aspects of epithermal neutron activation analysis (ENAA) and fast-neutron-induced reaction interferences in conventional instrumental thermal neutron activation analysis (TNAA) have been considered. A new generalized advantage factor which reflects a practical improvement of detection limits in ENAA is proposed. In the determination of practical advantage factors, consideration is also given to the different irradiation channels available for the experiment in a given reactor, or even in several accessible reactors. Fast neutron reaction interference factors are tabulated for both ENAA and TNAA and examples are given of specific interferences in TNAA for some biological and geological matrices.     

Photo-oxidative stability of electron beam and UV cured acrylated epoxy and urethane acrylate resin films

The post-cured photo-oxidative stability of urethane and bisphenol-A epoxyacrylate resins in mixed compositions with triacrylate and amine diacrylate resins are examined using UV and reflectance infra-red absorption spectroscopic techniques. Overall, by measuring the growth in hydroxyl absorption at 3400 cm⁻¹, electron-beam cured resin films are more photostable than UV curedfilms, indicating the high photo-activity of residual photoinitiator in the latter case. Regarding the UV cured systems benzophenone is found to be a more photo-active residual photoinitiator than the benzoyl ester photofragmenting types. Films containing the amine diacrylate resin are more photostable than those containing the triacrylate resin. This stabilising effect is associated with the oxygen and radical scavenging ability of the terminal amine groups. Photo-yellowing, as measured by the growth in an absorption band at 280 nm, is observed only in resin films containing the amine diacrylate resin and is associated with the formation of unsaturated carbonyl groups. The latter are, however, photobleached on prolonged irradiation whereas with resins containing the bisphenol-A epoxy acrylate resin, a longer term photo-yellowing is observed due to oxidation of the bisphenol-A to give stilbene-quinone products.     

Characterization in the Toughening Process of CTBN Modified Epoxy Resins Induced by Electron Beam Radiation

Epoxy resins are widely utilized as high performance thermosetting resins for many industrial applications but characterized by a relatively low toughness. Electron beam (EB) curing of polymer resins has a number of advantages over conventional thermal curing, such as shorter curing time, low energy consumption, low cure temperature, dimensional stability, reduced manufacturing cost. In the present work liquid carboxyl-terminated butadiene acrylonitrile (CTBN) copolymers containing 8% acrylonitrile is added at different contents to improve the toughness of diglycidyl ether of bisphenol A (DGEBA) epoxy resins using triarylsulfonium hexafluoroanimonate as a photointiator. The EB irradiation was conducted 5 kGy to 250 kGy in nitrogen. The physics properties of CTBN modified epoxy resins were examined by determine gel content, DMA (dynamic mechanical analysis), UTM (Instron model 4443), SEM (scanning electron microscopy).     

Phototoxic effect of visible light on Porphyromonas gingivalis and Fusobacterium nucleatum: an in vitro study

The antibacterial effect of visible light irradiation combined with photosensitizers has been reported. The objective of this was to test the effect of visible light irradiation without photosensitizers on the viability of oral microorganisms. Strains of Porphyromonas gingivalis, Fusobacterium nucleatum, Streptococcus mutans and Streptococcus faecalis in suspension or grown on agar were exposed to visible light at wavelengths of 400-500 nm. These wavelengths are used to photopolymerize composite resins widely used for dental restoration. Three photocuring light sources, quartz-tungsten-halogen lamp, light-emitting diode and plasma-arc, at power densities between 260 and 1300 mW/cm2 were used for up to 3 min. Bacterial samples were also exposed to a near-infrared diode laser (wavelength, 830 nm), using identical irradiation parameters for comparison. The results show that blue light sources exert a phototoxic effect on P. gingivalis and F. nucleatum. The minimal inhibitory dose for P. gingivalis and F. nucleatum was 16-62 J/cm2, a value significantly lower than that for S. mutans and S. faecalis (159-212 J/cm2). Near-infrared diode laser irradiation did not affect any of the bacteria tested. Our results suggest that visible light sources without exogenous photosensitizers have a phototoxic effect mainly on Gram-negative periodontal pathogens.