Thermal and thermo-oxidative degradation of high density polyethylene/fullerene composites

Fullerene (C₆₀)/high density polyethylene (HDPE) composites were studied in order to understand for their behaviors on thermal and thermo-oxidative degradation. Under different atmosphere, the influences of C₆₀ on the thermal stability of HDPE are different. Thermogravimetric analysis coupled to Fourier transform infrared spectroscopy (TG-FTIR) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) demonstrate that in N₂ the addition of C₆₀ increases the onset decomposition temperature by about 10 °C with more heavy compounds (more than 34 carbon). Also the thermal stability of HDPE in air is remarkably improved with the addition of C₆₀. When the content of C₆₀ is 2.5 wt% the onset decomposition temperature increases by about 91 °C. The results of viscoelastic behavior and gel content reveal that C₆₀ can trap the alkyl radicals and alkyl peroxide radicals to inhibit hydrogen abstraction to suppress the chain scission and preserve the long chain structure. However, in the absence of C₆₀ or with low C₆₀ concentration, hydrogen abstraction occurs, resulting in the formation of a series of alkyl radicals and alkyl peroxide radicals, which accelerates the chain scission and plays a leading role in the thermal oxidative degradation.     

The kinetics of thermo-oxidative humic acids degradation studied by isoconversional methods

Humic acids represent a complicated mixture of miscellaneous molecules formed as a product of mostly microbial degradation of dead plant tissues and animal bodies. In this work, lignite humic acids were enriched by model compounds and the model-free method suggested by Šimon was used to evaluate their stability over the whole range of conversions during the first thermooxidative degradation step. The kinetic parameters obtained were used to predict the stability at 20 and 180°C, respectively, which served for the recognition of processes induced by heat and those naturally occurring at lower temperatures. Comparison of the conversion times brought a partial insight into the kinetics and consequently into the role of individual compounds in the thermooxidative degradation/stability of the secondary structure of humic acids. It has been demonstrated that aromatic compounds added to humic acids, except pyridine, increased stability of humic acids and intermediate chars. The same conclusion can be drawn for acetic and palmitic acids. Addition of glucose or ethanol decreased the overall humic stability; however, the char of the former showed the highest stability after 40% of degradation.     

Kinetics of chlorine-induced polyethylene degradation in water pipes

The presence of chlorine in drinking water supplies in many countries creates the undesirable side effect of causing a relatively under investigated degree of polymer degradation in the polyethylene pipes used for transport. In order to predict pipe lifetimes and ensure safe water supplies, a kinetic model using data for the degradation rates of polyethylenes immersed in chlorine solutions, was developed. In order to replicate phenomena that normally occur very slowly at low concentrations of chlorine, accelerated ageing studies were necessary. These were carried out at high chlorine concentrations under well-defined experimental conditions (70, 400 and 4000 ppm). Results showed that, for the chlorine concentrations studied, a chain scission process associated with carbonyl formation is occurring. It was also shown that the rate of this degradation does not depend on the presence of stabilizer. A kinetic model, taking into account the chlorine concentration, is proposed in order to simulate the molar mass changes occurring. This will facilitate the prediction of the degree of polyethylene embrittlement and ultimately the lifetime.     

Influence of fullerene on the kinetics of thermal and thermo-oxidative degradation of high-density polyethylene by capturing free radicals

The influence of fullerene (C₆₀) on the thermal and thermal-oxidative degradation of high-density polyethylene (HDPE) was studied using non-isothermal thermogravimetric analysis under nitrogen (N₂) and air atmosphere. Kinetic parameters of the degradation were evaluated using the Flynn–Wall–Ozawa method, which does not require the knowledge of the reaction mechanism. The results showed that the addition of C₆₀ enhanced the thermal stability of HDPE and increased the activation energy both in N₂ and air atmosphere and especially affected the initial stage of degradation. In N₂, C₆₀-trapped carbon-centered radical originated from the degradation of HDPE to improve the thermal stability and increase the activation energy. While in air, C₆₀ trapped the alkyl radicals and alkyl peroxide radicals to inhibit the hydrogen abstraction (especially the initial stage of thermo-oxidative degradation) and form more stable species, which improved the thermal stability and increased the activation energy during the thermal degradation of HDPE. Comparing with that of pure HDPE, the changes of activation energy for HDPE/C₆₀ nanocomposites were higher in air than in N₂, especially in the initial stage.     

Monitoring thermo-oxidative degradation of polypropylene by CRYSTAF and SEC-FTIR

Samples of a polypropylene homopolymer have been degraded and analysed with regard to chemical composition, molecular weight distribution and chemical composition distribution. FTIR shows the progress of degradation and a decrease in molecular weight can be observed from SEC. CRYSTAF shows that the chemical heterogeneity of the samples broadens with continuing degradation. SEC-FTIR reveals that the degraded species are mainly found in the low molecular end of the molecular weight distribution. The spatial heterogeneity of the degradation process has been proven by the analysis of abrased layers.     

Improvement of the thermo-oxidative stability of low-density polyethylene films by organic-inorganic hybrid coatings

LDPE films have been coated with single or bi-layer hybrid coatings formed through sol-gel reactions in order to improve their thermo-oxidative resistance. Different chemical compositions of the coating were investigated which differ either in the amount of the inorganic phase (silica deriving from tetraethoxysilane) or in the organic component (either alkoxy silane functionalized polyethylene-poly(ethylene glycol) diblock copolymers or poly(vinyl alcohol)). The thermo-oxidative stability of the coated films thus obtained has been assessed by means of isothermal differential scanning calorimetry (DSC) and isothermal thermo-gravimetric analysis (TGA) under accelerated conditions, i.e. at high temperatures in pure oxygen flow. Conventional ageing in air at lower temperature, slightly above the in-service one, has also been carried out. The obtained data show: a) a general improvement of the thermal-resistance for the coated LDPE samples; b) a particularly high thermal-resistance for LDPE coated with a bi-layer coating with pure silica in the top layer; c) the effectiveness of the accelerated techniques in qualitatively assessing the thermo-oxidative resistance of the coated polymeric systems.     

A survey of methods for the detection of thermal oxidation in high-density polyethylene pipes

Seven methods for the detection of thermal oxidation of the inner wall surface of high-density polyethylene (HDPE) pipes are presented. The methods presented include infrared spectroscopy, polarized light microscopy, differential scanning calorimetry, scanning electron microscopy, gloss measurements and uniaxial creep tests. These tests have been developed on the basis of earlier reported data for a large number of PE pipes. The tests are compared with each other and with the internal pressurizing test with respect to reliability of results, the time taken to determine whether or not a pipe is oxidized, the experimental difficulties, costs, etc.     

Influence of temperature on the thermo-oxidative degradation of polyamide 6 films

The thermo-oxidative degradation of polyamide 6 (PA6) was studied at relative high temperatures (between 120 and 170 °C) using oxygen uptake and hydroperoxide determination methods, chemiluminescence, FT-IR and UV-VIS spectroscopy as well as solution viscosity and tensile property measurements.The relation between the results of the different analytical techniques and influence of temperature on these relations was determined. Arrhenius plots of the degradation determined with the different methods are linear; however the activation energies determined from these plots depend on the analytical method used. For oxygen uptake measurements and changes in UV absorbance (at 280 nm) and solution viscosity an activation energy of about 120 kJ/mol was calculated, for the increase in carbonyl index of about 80 kJ/mol and for the decrease in elongation at break of about 150 kJ/mol.The changes in oxygen uptake UV absorbance and solution viscosity are probably due to the same chemical process. The lower activation energy from changes in the carbonyl index is attributed to the formation of gaseous products, which play a larger role at higher temperatures. The higher activation energy from the elongation at break measurements was ascribed to the contribution of physical changes that play the largest role at the highest temperatures.     

Degradation and stabilisation of poly(ethylene-stat-vinyl acetate): 1 - Spectroscopic and rheological examination of thermal and thermo-oxidative degradation mechanisms

The degradation of ethylene vinyl acetate (EVA) copolymers was compared with low density polyethylene (LDPE), poly(vinyl acetate) (PVAc) and poly(vinyl chloride) (PVC) using FTIR, UV-visible and fluorescence spectroscopy as well as thermal and rheological analyses. Thermal, thermo-oxidative and photo-oxidative studies were conducted. Thermo-oxidation below 180 °C shows more similarities between EVA and LDPE. The luminescence spectra of degraded EVA and LDPE were almost identical but very different to that of PVAc. UV-vis analysis showed that the polyenes present in aged PVC were unlikely to be the same species responsible for the observed colour formation in aged EVA. It is suggested that they are polyconjugated carbonyl products. Rheological analysis also showed the evolution of crosslinking reactions during thermo-oxidation. FTIR studies after thermal degradation in inert conditions 290 °C showed complete loss of the ester functionality and associated lactone formation along with some evidence for ketonic and unsaturated carbonyl groups. Degradation in air at 180 °C, however, revealed that loss of the ester group was not so marked, with PVAc exhibiting the greatest stability. This was in line with the induction time to onset of autocatalytic carbonyl growth at 180 °C; the latter showed an apparent exponential decrease with increasing vinyl acetate content up to 28% w/w. Fluorescence analysis produced trends that complemented those of carbonyl index; the time to decomposition of initial fluorescent α,β-unsaturated carbonyl species coincided with the time to onset of carbonyl growth. Furthermore, the rate of formation of the new fluorescent species produced in EVA, and LDPE was similar to that of carbonyl growth. These new fluorescent species are therefore likely to be di- or tri-carbonyl products.     

氧化镧对HDPE热氧化分解行为的影响

聚合物改性是聚合物结构与性能研究中的一个重要领域,而稀土元素具有4f0-145dl-106s2的电子构型,由于4f轨道的特殊性和5d轨道的存在,稀土离子具有丰富的电子能级,离子半径较大,电荷较高,又有较强的络合能力,可对多种聚合物的热稳定性产生影响[1,7].     

Monitoring the influence of different weathering conditions on polyethylene pipes by IR-microscopy

Plastic pipes are often exposed to a range of environmental conditions which may lead to their degradation. The most important influence factors are UV radiation, humidity and temperature. These can cause leaching of long-term and light stabilisers and finally oxidation of the polymer. In this study we demonstrate how the elemental steps of the photooxidative degradation of polyethylene pipes can be monitored by IR-microscopy. In detail the influence of UV radiation leads to a depletion of the phenolic long-term stabiliser, Irganox 1010. Calibration of the spectroscopic data enables IR-microscopy to be carried out in a quantitative manner and the rate constants for the stabiliser loss to be calculated for the first time. The results obtained from IR-microscopy are well in agreement with those obtained by mechanical sample preparation and measurement of the oxidative induction time (OIT) as well as extraction coupled with chromatographic analysis (HPLC). A mechanism based on Norrish type cleavage is proposed. Also the formation of trans-vinylidene groups as unsaturated degradation products of the PE can be observed. In summary it can be shown that IR-microscopy is highly superior to the conventional approach of mechanical sample preparation with regard to spatial resolution and offers the advantage of being less labour intensive.     

Effect of organophosphate antioxidant on the thermo-oxidative degradation of a mineral oil

This study shows the synthesis, characterization, and evaluation of the effect of organophosphate antioxidant on the thermo-oxidative degradation of a mineral oil. The organophosphate was synthesized by nucleophilic substitution (S_N2) of hydrogenated cardanol. For this study, were employed thermogravimetry, derivative thermogravimetry, differential scanning calorimetry, and differential thermal analysis techniques. The results showed that organophosphate contributed for thermo-oxidative stability of mineral oil (initial decomposition temperature (IDT) mineral oil: 91.28 °C < IDT mineral oil + organophosphate (1%): 156.42 °C). The organophosphate obtained shows significant thermal stability when compared with other compound of the same class (diphenyl phosphate).     

Catalytic degradation of polyethylene evaluated by TG

HZSM-5 zeolite was screened as catalyst for high density polyethylene degradation at 450C, under nitrogen static atmosphere. Two different samples were studied in this condition: HDPE alone and mixed with HZSM-5. The reactor was connected on line to an HP 5890-II gas Chromatograph. Sample degradation was investigated using a Perkin-Elmer Delta 7 Thermobalance, from room temperature to 800C, with heating rates of 5.0, 10.0 and 20.0C min^–1. From TG curves, the activation energies, calculated using an integral kinetic method, decreased 60.6% in the presence of the zeolite.This work was supported by Conselho Nacional de Desenvolvimento Cientifico e Tecnológico (CNPq) and CoordenaÇÃo de Apoio ao Pessoal de Ensino Superior (CAPES).     

Effect of stereoregularity on the thermo-oxidative degradation of poly(propylene)s estimated by chemiluminescence

The effect of stereoregularity on the thermo-oxidative degradation of poly(propylene)s, isotactic (IPP) and syndiotactic (SPP), was compared with that of high density polyethylene (HDPE) by means of chemiluminescence (CL). SPP is extremely stable to thermal oxidation and CL signals appeared much later than in IPP and even later than in HDPE. For example, at 160°C the maximum intensity of CL was measured after only 13 min for IPP, 60 min for HDPE and 260 min for SPP. IR spectroscopic results support the conclusions drawn from CL results.     

Thermal and thermo-oxidative degradation of polystyrene in the presence of bromine-containing flame retardants

The kinetic of thermal and thermo-oxidative degradation of polystyrene in the presence of bromine-containing flame retardants was investigated. It was shown that the kinetics is limited by diffusion in air and by the processes occurring at the interface in helium.The flame retardants affect the degradation of polystyrene both chemically and physically, and change the mechanism of the limiting stage to some extent.

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Zusammenfassung Die Kinetik des thermischen und thermo-oxidativen Abbaus von Polystyren in Gegenwart bromhaltiger Flammschutzmittel wurde untersucht. Es wird gezeigt, dass die Reaktion durch die Diffusion in Luft bzw. durch die Grenzflächenvorgänge in Helium begrenzt wird.Die Flammschutzmittel beeinflussen den Abbau von Polystyren sowohl chemisch als auch physikalisch und verändern im gewissen Masse auch den Mechanismus des geschwindigkeitsbestimmenden Schritts.

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Correlation of humic substances chemical properties and their thermo-oxidative degradation kinetics

Application of the Arrhenius equation as the temperature function in modeling of the degradation kinetics of humic substances brought a high positive Pearson correlation coefficient with the carbon content and a reasonable negative correlation with the oxygen content. Ratio C/H indicating the aromaticity degree of humic samples did not show any significant correlation. Relatively high value of correlation coefficients provided also O + N and ratios C/(O + N) and C/O, respectively. In contrast, H, N content and natural and heat generated free radical content and their ratio gave substantially lower correlation coefficients. The latter indicates that free radicals are probably not the main reason of the collapse of the secondary structure of humic substances leading to their degradation.     

Understanding of thermal/thermo-oxidative degradation kinetics of polythiophene nanoparticles

The polythiophene nanoparticles (nano-PT) were prepared with average diameter of 20–35 nm. The nanostructurals of polythiophene were confirmed by TEM and SEM analyzes. The kinetics of the thermal degradation and thermal oxidative degradation of nano-PT were investigated by thermogravimetric analysis. Kissinger method, Flynn–Wall–Ozawa method, and advanced isoconversional method have been used to determine the activation energies of nano-PT degradation. The results showed that the thermal stability of nano-PT in pure N₂ is higher than that in air atmosphere. The analyzes of the solid-state processes mechanism of nano-PT by Criado et al. method showed: the thermal degradation process of nano-PT goes to a mechanism involving second-order (F ₂ mechanism); otherwise, the thermo-oxidative degradation process of nano-PT is corresponding to a phase boundary controlled reaction mechanism (R ₂ mechanism).     

Characterisation of polysilanes by thermal analysis methods

Polysilanes have been synthesised as potential precursors for silicon carbide fibres. One critical property of these precursors is the ceramic yield obtained on pyrolysis. This is determined by TG and typical curves are shown. A second important property is the suitability for spinning a fine, flexible fibre. The characterisation of ‘spinnability’ is subjective but one of the aims of this work has been to define more precisely the temperature at which to attempt spinning. This has involved the use of TMA and DSC.     

Covalent binding of polyethylene glycol to the surface of red blood cells as detected and followed up by cell electrophoresis and rheological methods

Cyanuric chloride activated polyethylene glycol (PEG)-5000 was covalently coupled to murine and human red blood cells (pegylated RBC). Our purpose was to camouflage RBC receptors, which is necessary for parasite invasion, a process essential to sustain parasitemia. Cell electrophoretic mobility analysis (CEM) of pegylated RBC distinguished a new population of cells bearing characteristic CEM. Pegylation of RBC also modified their rheological properties, which were documented by evaluation of cell deformability (based on cell transit time through calibrated micropores) and cell aggregation (as measured by ultrasonic interferometry). Homologous transfusion of pegylated RBC into murine malaria-infected mice had no significant effect on the cerebral malaria death rate in Plasmodium berghei-infected mice, but it reduced the peripheral blood parasitemia by a factor 2 while in Plasmodium yoelii infected mice, the parasitemia was dramatically reduced by a factor of 4. These experiments demonstrate that transfusion of pegylated RBC may inhibit peripheral parasitemia. Cell electrophoresis appears to be a useful tool to allow in vivo detection and to investigate the fate of transfused pegylated RBC.     

The thermo-oxidative degradation of polyolefines—Part 10. Correlation between the formation of carboxyl groups and scission in the oxidation of polyethylene in the melt phase

Films of low density polyethylene have been degraded under an oxygen atmosphere at temperatures above the semicrystalline melting point. Time, conversion and temperature dependence of carboxyl group formation and chain scission have been studied. After induction periods we found linear dependences both in function of time and conversion. One third of absorbed oxygen forms carboxyl groups and the absorption of 3·57 mmol oxygen per monomer unit is needed for one chain scission. Maximum rates of carboxyl formation and chain scission have Arrhenius temperature dependence with 33·5 kcal/mole activation energy. The number of carboxyl groups and chain scissions are always practically the same; we assume that the isomerisation of secondary alkyl peroxy radicals simultaneously causes chain scission and carboxyl formation.