Investigation of free volume and the interfacial,and toughening behavior for epoxy resin/rubber composites by positron annihilation

An epoxy resin (EP) matrix has been modified with carboxyl-randomized butadiene-acrylonitrile (CRBN) rubber and hydroxyl-terminated butadiene-acrylonitrile rubber (HTBN). When the rubber content was low (⩽5%), the free volume size varied slowly, meanwhile, the free volume size of EP/HTBN system was smaller than EP/CRBN system. With further addition of rubber component (⩾7%), the free volume size of the composite increased quickly. In this case, the free volume size of EP/HTBN system was larger than EP/CRBN system. The intermediate positron lifetime component (I₂) was affected by the structure of the interface layer between rubber particles and EP matrix. The different free volume properties could be attributed to the compatibility between rubber and EP.     

Influence of structure of a crosslinked epoxy resin on its properties studied by positron annihilation and other methods

Positron annihilation has been applied to study samples of two crosslinked epoxy resins: onglycidyl ether of bisphenol A (Epikote 828) and polyglycidyl-ether of phenol-formaldehyde novolac (Epikote 155) cured with 4,4-diamino-diphenylo-methane (MDA), phenol-formaldehyde novolac resin (Novolac Z) and bisphenol A (formaldehyde resin). Results of measurements of positron lifetime spectra were compared with the ones coming from DMTA, flexural strength testing and density measurements. The most important features of samples (glass transition temperature, storage modulus, flexural strength, crosslinking density and tan proved to be correlated with the product , proportional to the fractional free volume in samples. Values of have been estimated from the values of ₃, the longest lifetime in positron lifetime spectra.I ₃ corresponds to the intensity of the longest-lived component in them. Distributions of free volume radii reconstructed on the basis of PAL measurements are given for all samples. The influence of structure of both cured resin and the curing agent on the properties of the crosslinked products is clearly seen from the presented results.     

Study of the photodegradation of epoxy polymers with slow positron annihilation spectroscopy

The photodegradation of an amine‐cured epoxy coating after exposure to accelerated UV‐340 and UV‐313 irradiation was investigated with an atomic‐level technique, positron annihilation spectroscopy (PAS), which detected and characterized the free volumes and defects as a function of the depth. Significant changes in the subnanometer defect parameters S and W were observed as a function of the exposure time near the surface. This was interpreted as due to a loss of the free volume and hole fraction resulting from photodegradation. A dead layer near the surface, resulting from UV irradiation from the surface up to a thickness of 0.4 μm, at which there was nearly no positronium formation, was observed. Correlations between physical defects from PAS in terms of the free volumes and chemical defects from electron spin resonance spectroscopy in terms of free radicals and chemical structural changes measured by ultraviolet–visible and Fourier transform infrared spectroscopy were established. A high sensitivity of PAS for detecting the early stage of degradation, on the order of hours for UV‐313 and on the order of days for UV‐340 irradiation, was observed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2441–2459, 2004     

Electrical and positron annihilation study on epoxy and epoxy acrylate composites

Epoxy acrylate resin was prepared by endcapping the acrylic acid to epoxy resin backbone in the presence of triphenyl phosphene as catalyst. The structure was elucidated by IR and NMR spectroscopy. Epoxy and epoxy acrylate composites were prepared by mixing different concentrations of mica, magnesium hydroxide and calcium silicate with each epoxy/hardener and epoxy acrylate/styrene mixtures, respectively. The permittivity ε′, dielectric loss ε′′ and loss tangent tan δ were measured for these composites in the frequency range (10²-10⁶ Hz) and at 30 °C. The data obtained were analyzed into two absorption regions related to Maxwell-Wagner effect and to some local molecular motions rather than the main chain motion. The higher values of ε′ and the lower values of tan δ given for the composites containing the epoxy acrylate resin indicate some improvement in the dielectric properties when compared with those containing the epoxy resin. The effect of filler type and filler content on the positron annihilation lifetime and its intensity as well as S-parameter for epoxy and epoxy acrylate composites were also studied. The high values of S-parameter noticed by with increasing filler content indicates some increase in free electrons which lead to an increase in electrical conductivity. The highest value of hardness was obtained in the case of calcium silicate followed by mica and magnesium hydroxide.     

Study on the microstructure and mechanical properties for epoxy resin/montmorillonite nanocomposites by positron

Positron annihilation lifetimes have been measured for epoxy resin/organic montmorillonite (OMMT) nanocomposites. Effects of different dispersion states of nano-layered OMMT on the positron annihilation parameters and the mechanical properties were studied. We found that the ortho-positronium (o-Ps) intensity decreased with increasing OMMT content, which indicated that the interaction between the host and nanofillers restrained the segmental motion, resulting in a decrease of the free volume. On the other hand, it is very interesting to observe a good correlation between the interfacial interaction and mechanical properties, suggesting that the dispersion states of OMMT and interfacial property between clay layers and matrix played an important role in determining the mechanical properties.     

Study of the association of toluene by positron annihilation

Theoretical and Experimental Chemistry -     

Creep behavior of epoxy resin during irradiation at cryogenic temperature

Creep tests of an epoxy resin during bending and irradiation have been carried out to investigate the synergistic effects of radiation and stress on mechanical properties of the resin. Simultaneous application of stress and irradiation on the epoxy resin enhanced creep rates in comparison with the application of stress on an irradiated sample. In order to clarify the mechanism of the radiation-induced creep, measurements of solvent swelling of specimens have been performed. The swelling increased with the dose and the increase of the swelling corresponds to the increase of the chain scission. The mechanism of increased deformation of the resin during irradiation is proposed to be caused by increased chain scission following the release of the local strain energy.     

Investigation of nonsolvated electron reactions by means of the positron annihilation method

The validity of a model developed by us in which the positronium precursor is mainly the nonsolvated electron makes it possible to study the reactivity of nonsolvated electrons using data on positronium formation probabilities in solutions of electron acceptors. The rate constants thus obtained agree in most cases with those determined with picosecond pulse radiolysis techniques.     

Study of relaxation processes in polyethylene and polystyrene by positron annihilation

Relaxation processes in polyethylene (PE) and polystyrene (PS) were studied by positron annihilation technique. For PE, above the glass transition temperature, T_g, the size of free volumes and its concentration were increased by the micro-Brownian motion of molecules. For PS, local motions of molecules in backbone chains were found to start above 260 K. However, these local motions were suppressed by an interphenyl correlation. For both PE and PS, below 250–260 K, the formation probability of positronium atoms increased with decreasing temperature. This fact was assigned to the freezing in of the local motions of molecules. For PS, an onset of the local motions of molecules was observed above 100 K. These motions were expected to be associated with liberation of phenyl groups. © 1996 John Wiley & Sons, Inc.     

环氧树脂在热塑性树脂改性中的应用

本文综述了国内外有关利用环氧树脂改性热塑性树脂共混体系研究的最新进展。着重阐述了环氧树脂在热塑性树脂之间的增容作用,如尼龙6(PA6)合金体系,改性聚苯乙烯塑料(ABS)合金体系,以及聚对苯二甲酸丙二醇酯(PTT)合金体系等。同时,介绍了利用环氧树脂的反应活性提高无机填料在聚合物中分散性研究的情况,如二氧化硅纳米粒子在聚醚砜(PES)中,以及滑石粉在聚丙烯(PP)中分散性的提高。最后,简介了环氧树脂改性热塑性树脂提高热塑性树脂物理机械性能方面的研究方向和成果并展望了环氧树脂在热塑性树脂改性研究中的前景。     

Free volumes in polystyrene probed by positron annihilation

Free volume characteristics in three samples of monodisperse polystyrene were investigated by positron annihilation technique over a temperature range from 300 to 380 K. The number-average molecular weight of the samples ranged from 5730 to 1,524,000. The observed lifetime spectra were resolved into three components, where the longest lifetime, τ₃ was associated with the pick-off annihilation of ortho-positronium (o-Ps) trapped by free volumes. The change of the temperature coefficient of τ₃ was observed at around 350 K, at which the value of τ₃ was a constant value of 2,3 ns for all specimens with different molecular weights. There was no discrete change of τ₃ in intensity, which is corresponding to the number of free volumes. The size of free volume at glass transition was evaluated to be 0.l nm³. © 1996 John Wiley & Sons, Inc.     

Study of water in Ca-montmorillonite by thermal analysis and positron annihilation lifetime spectroscopy

Journal of Thermal Analysis and Calorimetry - The aim of this study is to characterize adsorbed liquid in montmorillonite structure for different levels of adsorption by both thermoanalytical and...     

Effect of electric field strength and exposure time on epoxy and high density polyethylene measured by positron annihilation lifetime

Using the positron annihilation lifetime technique, the annihilation parameters have been measured for epoxy and high density polyethylene (HDPE) as a function of AC electric field strength and the exposure time. The lifetime spectra have been resolved into three components, the longest component (I₃₃) is attributed to the pick-off annihilation of o-Ps in the amorphous regions. The intermediate one (I₂₂) is due to the annihilation of free positrons, while the shorter component (I₁₁) stems from self annihilation of p-Ps. In HDPE, the o-Ps parameters ₃ andI ₃ are measured as a function of electric field strengths in the range from 10 to 100 kV/cm exposed for 24 hours. A decrease inI ₃ of 8% is observed from zero to 50 kV/cm followed by an increase of the same order from 50 to 100 kV/cm. By investigating the effect of the exposure time from 2 to 24 hours at 16 and 50 kV/cm, the effect is confirmed and is attributed to the inhibition of o-Ps formation at lower field strength. In epoxy, the effect or exposure time onI ₃ at 166 and 133 kV/cm shows a similar behavior as in HDPE. At 133 kV/cmI ₃ decreases by only 2.5%. On the other hand, the changes in ₃ occur at short exposure times. Again at large times the saturation is obtained. These effects are attributed to the expansion of free volume (increase of ₃) competing at longer exposure times with other phenomena, such as liberation of free radicals, which reduce the o-Ps intensityI ₃ through the conversion to p-Ps. The reactions between o-Ps and free radicals might also lead to free positrons, which could explain the increase ofI ₂ and the decrease of ₃ at longer exposure times.     

Free volume of cyanate resins studied by positron annihilation

The polymerization process of bisphenol-A dicyanate (BADCy) has been studied using a positron-annihilation lifetime technique (PAL). The polymerization was conducted at 150°C, and the process was followed by PAL. Seven kinds of samples with different curing times were also formed at 150°C, and the relation between the period of the curing time and the degree of polymerization was studied. It has been shown that theo-Ps lifetime increases in samples with a higher polymerization than 85%, which is consistent with measurements of the specific volume of BADCy.     

Micro-structure of gamma-ray irradiated polyethylenes studied by positron annihilation

Effects of gamma-ray irradiation on high density (HDPE) and low density (LDPE) polyethylenes were measured by positron annihilation at temperatures between 100 and 420 K. The effect of the irradiation on the intensity I₃ and the lifetime τ₃ of the longest lived component was significant below the glass transition temperature T_g, while they were little affected above T_g. For LDPE a marked minimum was observed in the I₃ vs T curve. The lower edge of the minimum, corresponding to glass II and glass I transitions, was found to shift to lower temperatures by the irradiation. In HDPE both I₃ and τ₃ decreased on irradiation mainly due to radiation induced free radicals. The gel fraction of HDPE was small when irradiated below T_m, while it rose sharply on irradiation near T_m. Positron lifetime parameters of this highly crosslinked HDPE showed a distinct difference compared to HDPE irradiated below T_m. Usefulness of the positron annihilation method is discussed in conjunction with studying micro-structure of polymers.     

Vacuum removal of the template in MCM-41 silica studied by the positron annihilation method

Positron annihilation lifetime spectra were measured for ordered silica before template (octadecyltrimethyl ammonium) removal. An intermediate lifetime component, well pronounced in the spectra, indicates the presence of structural defects in the template being the size of a surfactant molecule. At the temperature near 420 K a radical change of template structure occurs, consisting in appearance of disorder and the degradation of template; evaporation of the fragments begins. It seems that moderate heating (up to about 500 K only) in vacuum for several hours is an effective and simple method of template removal, leaving no pure carbon residue in the pore structure. The results are compared with the data from the liquid nitrogen adsorption/desorption method and elemental analysis, confirming the positron annihilation results.     

Evaluation of positron annihilation in Beryllium

A band theoretical calculation of angular distribution of annihilation photons (ADAP ) and the positron lifetime, up to and including higher momentum components is reported. The results obtained using biquadratic quasianalytic integration schemes for all Brillouin zone integrals, compare favorably with existing experimental data. There are, however, significant structures in the ADAP curve obtained than in the experimental curves.     

Path integral methods of positron annihilation

The problem of computing the properties of a low mass quantum particle in equilibrium in a disordered medium is considered. With the advancement of computational speed, statistical methods for sampling a complex phase space are now viable. The Feynman-Kac path integral establishes a connection between a quantum particle and classical polymer consisting of p atoms. This allows the computation of quantum mechanical equilibrium values using well known methods devised for classical systems. Here we review the application of the path integral to the computation the properties of thermalized positron and positronium and introduce some new directions of investigation.     

Temperature dependence of positron annihilation lifetime spectra for polyethylene: positron irradiation effects

Lifetime spectra for linear and branched polyethylene have been measured as a function of temperature. The longest lifetime, τ₃, and its intensity, I₃, are traced over a temperature range of 105–370 K. The lifetime decreases with decreasing temperature, and upon reheating the plot is retraced. I₃ has a minimum near 265 K with considerable hysteresis in the cooling/heating cycle. At the lower temperatures the increase in I₃ is attributed to source irradiation.