DSC monitoring of supermolecular structure damage of polyethylene products

Investigated materials were produced from polyethylene of low density (PE-LD) and a filler: carbon black or chalk. A part of the samples was kept in ambient temperature over several months in order to study the effect of material ageing. The qualitative conclusions were drawn based on a precise analysis of shape of DSC curves and the basic investigations of PE morphologies known from literature. The influence of the thermal history and the filler contents on the amount and kind of crystal phase was established. Additionally, the effect of the measurement technique, in our case it was positron annihilation lifetime spectroscopy (PALS), on the morphological feature changes was found. The paper serves selected examples of problems solved by DSC. However, from the other hand, the authors discuss critically the opportunity given by this method.     

Spherical silica particles decorated with graphene oxide nanosheets as a new sorbent in inorganic trace analysis

Graphene oxide (GO) is a novel material with excellent adsorptive properties. However, the very small particles of GO can cause serious problems is solid-phase extraction (SPE) such as the high pressure in SPE system and the adsorbent loss through pores of frit. These problems can be overcome by covalently binding GO nanosheets to a support. In this paper, GO was covalently bonded to spherical silica by coupling the amino groups of spherical aminosilica and the carboxyl groups of GO (GO@SiO₂). The successful immobilization of GO nanosheets on the aminosilica was confirmed by scanning electron microscopy and X-ray photoelectron spectroscopy. The spherical particle covered by GO with crumpled silk wave-like carbon sheets are an ideal sorbent for SPE of metal ions. The wrinkled structure of the coating results in large surface area and a high extractive capacity. The adsorption bath experiment shows that Cu(II) and Pb(II) can be quantitatively adsorbed at pH 5.5 with maximum adsorption capacity of 6.0 and 13.6 mg g⁻¹, respectively. Such features of GO nanosheets as softness and flexibility allow achieving excellent contact with analyzed solution in flow-rate conditions. In consequence, the metal ions can be quantitatively preconcentrated from high volume of aqueous samples with excellent flow-rate. SPE column is very stable and several adsorption–elution cycles can be performed without any loss of adsorptive properties. The GO@SiO₂ was used for analysis of various water samples by flame atomic absorption spectrometry with excellent enrichment factors (200–250) and detection limits (0.084 and 0.27 ng mL⁻¹ for Cu(II) and Pb(II), respectively).     

The influence of the plasticization on free volume in polyvinyl chloride

Positron lifetime measurements in polyvinyl chloride (PVC), plasticized with the aid of dibutyl phthalate and tricresyl phosphate have been made. The plasticizers, the first range plasticizers, are an organic and an inorganic ester, respectively. The influence of the different concentration of the plasticizer in the PVC on positron lifetimes in the polymer have been investigated. A conventional fast-slow coincidence lifetime spectrometer with plastic scintillators has been used for the lifetime measurements. All the measurements have been performed in air, at room temperature. Mean free volumes radii have been calculated from the lifetime data.     

On the α relaxation of the constrained amorphous phase in poly(ethylene)

The idea of coexistence of two different amorphous fractions in semi-crystalline poly(ethylene) (PE) is taken into consideration. Differential scanning calorimetry, dynamic mechanical thermal analysis and positron annihilation were used to study the effect of supermolecular structure on the glass transition associated with ‘semi-ordered’ amorphous phase. The arrangement of chains, located in this phase, is forced internally by the presence of crystalline domains. Influence of drawing, irradiation and annealing on thermodynamic and structural parameters was investigated. In a series of experiments the correlation between the glass transition, the α relaxation and the free volume of a semi-crystalline system was found. In order to better describe the relaxation, existence of two types of amorphous fractions was assumed. The relaxations are treated as a long-scale motion of macromolecule segments located into the ‘semi-ordered’ amorphous regions, or into the ‘real’ amorphous regions, and are labelled as α_c and α_g, respectively. The magnitudes of the loss peaks were quite sensitive to the free volume, which was found to increase by drawing and decrease by irradiation. Two different DSC traces were recorded for both glass transitions.     

Triply fuzzy function approximation for hierarchical Bayesian inference

We prove that three independent fuzzy systems can uniformly approximate Bayesian posterior probability density functions by approximating the prior and likelihood probability densities as well as the hyperprior probability densities that underly the priors. This triply fuzzy function approximation extends the recent theorem for uniformly approximating the posterior density by approximating just the prior and likelihood densities. This approximation allows users to state priors and hyper-priors in words or rules as well as to adapt them from sample data. A fuzzy system with just two rules can exactly represent common closed-form probability densities so long as they are bounded. The function approximators can also be neural networks or any other type of uniform function approximator. Iterative fuzzy Bayesian inference can lead to rule explosion. We prove that conjugacy in the if-part set functions for prior, hyperprior, and likelihood fuzzy approximators reduces rule explosion. We also prove that a type of semi-conjugacy of if-part set functions for those fuzzy approximators results in fewer parameters in the fuzzy posterior approximator.     

Free volume in plasticized polyvinyl chloride

Positron lifetimes measurements in pure polyvinyl chloride (PVC) and in the plasticized PVC have been performed. Dioctyl phthalate has been used as a plasticizer. Samples have been prepared of the PVC with eight different plasticizer concentrations (from 0 to 35% of the plasticizer in the PVC). All of the measurements have been performed in air at room temperature. A conventional fast-slow coincidence lifetime spectrometer has been used for the measurements. Mean free volumes radii have been calculated from the lifetime data. It has been found that the mean free volumes radii are in the investigated region of plasticizer concentrations a linear function of the concentration of the dioctyl phthalate in the PVC. © 1996 John Wiley & Sons, Inc.     

Influence of the plasticization on free volume in polyvinyl chloride

Positron lifetime measurements in pure polyvinyl chloride (PVC) and in the plasticized PVC have been performed. Tricresyl phosphate was used as a plasticizer. Samples of the PVC were prepared with eight different plasticizer concentrations (from 0 to 35% of the plasticizer in the PVC). All of the measurements were performed in air at room temperature. A conventional fast–slow coincidence lifetime spectrometer was used for the measurements. Mean free volumes radii and fractional free volumes were calculated from the lifetime data. It has been found that the mean free volume radius is in the investigated region of the plasticizer concentrations, a linear function of the concentration of the tricresyl phosphate in the PVC. It seems that a polynomial fit can be used to describe the fractional free volume vs. the plasticizer concentration in the PVC. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1839–1845, 1998     

Thermal analysis and free volume study of polymeric supermolecular structures

Positron annihilation lifetime measurements were performed on samples cut down from commercially available polyethylene (PE) and poly(4-methyl-1-pentene) (PMP). The effect of a free volume on the segmental relaxation behaviour was examined. The samples were isothermally annealed at different temperatures. In order to study the effect of annealing on supermolecular structures of the polymers, the annealing temperatures were chosen between the polymers transition temperatures of the polymers. All thermodynamic parameters varied as compared to the parameters of the samples which were not annealed. A slight change of the free volume was observed. The idea of two miscellaneous amorphous fractions in polymer was under consideration. Differential scanning calorimetry, dynamic mechanical thermal analysis were used to study the effect of specimen heat treatment on both glass transitions, too. The degree of crystallinity of the PE and PMP samples was determined. An attempt to estimate this parameter from positron annihilation data was undertaken. This revised version was published online in July 2006 with corrections to the Cover Date.