Polymer Degradation and Stability (v.92, #11)

Calendar (I).

Flame retardant activity of SiO2-coated regenerated cellulose fibres by Silvo Hribernik; Majda Sfiligoj Smole; Karin Stana Kleinschek; Marjan Bele; Janez Jamnik; Miran Gaberscek (1957-1965).
An alternative route to lower the flammability of viscose fibres is presented. Instead of adding a flame retardant to the viscose dope chemically, we have grown a layer of silica (SiO2) on the surface of a regenerated cellulose fibre via a sol–gel process. One set of samples was used as-received, while the other was pre-treated in an 18% NaOH solution, giving a rough, etched surface to the fibre. The different surface morphology of both fibre types triggered a different growth of silica layers. On an untreated fibre, silica formed a 300–400 nm thick surface layer containing a high density of cracks and holes. Conversely, on a NaOH pre-treated fibre, the silica layer intruded into fibre interior, adhered more tightly to the fibre structure and formed an almost defect-free, thin (100 nm) layer on the outer fibre surface. This type of silica layer increased the temperature at which the fibre started to decompose by 20 °C. It also hindered significantly the flow of oxygen to the generated volatiles during the thermal decomposition, and increased the temperature of glowing combustion of the residual char; the temperature of the corresponding exothermic peaks increased by ca. 20 °C and 40 °C. In contrast, the thermal effects of silica coatings that grew on an untreated fibre were much smaller.
Keywords: Regenerated cellulose fibres; Thermal properties; Silica; Flame retardant;

Thermal stability of poly(methyl methacrylate)/silica nano- and microcomposites as investigated by dynamic-mechanical experiments by Nikolaos Katsikis; Franz Zahradnik; Anne Helmschrott; Helmut Münstedt; Andri Vital (1966-1976).
The thermal stability of poly(methyl methacrylate) (PMMA) filled with silicon dioxide particles was investigated by means of rheological tests. The change in the storage modulus G′ was measured, which is a very sensitive method to detect molecular changes in polymers. The long-term thermal stability of the composites was found to depend on the temperature of the melt, the size of the silica particles, which ranged from nano- to micrometers, and the volume fraction of the filler. For high temperatures and a large surface area of the silica particles the behaviour of the composites differs significantly from that of the pure polymer. Pure PMMA degrades at high temperatures, which correlates with a decrease of G′. In contrast an increase in G′ with increasing temperature and filler surface was measured for the composite materials. This behaviour is explained by chemical reactions of the PMMA molecules with the silica particles. Effects of that kind were not found for SiO2 filled polystyrene.
Keywords: Poly(methyl methacrylate); Silicon dioxide; Thermal stability; Time dependent; Storage modulus;

Mechanism of the temperature-dependent degradation of polyamide 66 films exposed to water by Elsa Silva Gonçalves; Lars Poulsen; Peter R. Ogilby (1977-1985).
Experiments were performed to elucidate the degradation mechanism of hot-pressed polyamide 66 upon exposure to water. For films exposed to water over the temperature range 25 °C–90 °C, degradation was monitored using FTIR and solid-state 13C NMR spectroscopies. The data are consistent with a mechanism in which (1) a radical is formed on the methylene carbon adjacent to the amide nitrogen, (2) this radical reacts with oxygen to form a hydroperoxide, and (3) the hydroperoxide decomposes to form an imide or a hydroxylated amide, both of which may cleave leading to chain scission. Water appears to facilitate degradation by increasing the flexibility of the polymer matrix through swelling rather than acting as a reactive species, at least at the early stages of the process. An apparent activation energy of 15 ± 2 kJ/mol is observed for the early stages of degradation, suggesting that segmental motions in the polymer associated with water and oxygen sorption or inter-chain radical reactions are indeed key components of the degradation process.
Keywords: FTIR; Oxygen; Polyamide 66; Water sorption; Radicals;

Thermo-oxygen degradation mechanisms of POSS/epoxy nanocomposites by Zengping Zhang; Aijuan Gu; Guozheng Liang; Penggang Ren; Jianqiang Xie; Xiaolei Wang (1986-1993).
A series of polyhedral oligomeric silsesquioxane/epoxy nanocomposites (POSS/EP) containing 0 wt%, 5 wt%, 10 wt% and 15 wt% content of POSS were prepared. Mechanical properties were used as the index to show the effect of POSS on the thermo-oxygen degradation resistance of epoxy resin. And the thermo-oxygen degradation mechanism was investigated by scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). Results showed that the incorporation of POSS into epoxy networks enhanced the thermo-oxygen resistance of epoxy. POSS led to the formation of inert layer on the surface of materials which could protect the internal structure from decomposition. As a result, the retention of mechanical properties of EP/POSS hybrids increased with the POSS content increasing.
Keywords: Polyhedral oligomeric silsesquioxane; Epoxy; Thermo-oxygen degradation resistance; Organic--inorganic hybrid materials; Nanocomposites;

Oxidative and enzymatic degradations of l-tyrosine based polyurethanes by Debanjan Sarkar; Stephanie T. Lopina (1994-2004).
Oxidative and enzymatic degradations of l-tyrosine based polyurethanes were studied for biomaterial applications. Oxidative degradation was performed with 0.1 M cobalt chloride (CoCl2) in hydrogen peroxide solutions at 37 °C and the degradation was assessed by ATR-FTIR. Results indicate that polyurethane with polyethylene glycol (PEG) shows soft segment degradation while polyurethane based on polycaprolactone (PCL) shows hard segment degradation. Enzymatic degradation of the polyurethanes was studied using proteolytic enzyme α-chymotrypsin in phosphate buffer solution (pH 7.4) at 37 °C. The enhanced degradability of l-tyrosine based polyurethanes is due to both the presence of amino acid based chain extender and the action of enzyme. The changes in the morphology of polyurethanes were analyzed by SEM. The results of the degradation study were correlated to the structure of the polyurethanes.
Keywords: Oxidation; Enzyme; Degradation; l-Tyrosine; Polyurethane;

Straight and helical carbon nanotubes with diameter from 20 to 60 nm have been synthesized through catalytic decomposition of polyethylene in autoclave at 700 °C. The X-ray power diffraction pattern indicates that the products are hexagonal graphite, and transmission electron microscope (TEM) and high resolution transmission electron microscope (HRTEM) images reveal the morphologies and structures of carbon nanotubes. The effects of reaction temperature, catalyst and maleated polypropylene on the growth of the carbon nanotubes were also discussed, and the growth mechanism of the CNTs was proposed. Pyrolysis of polyethylene is a promising green chemical method for economically producing carbon nanotubes.
Keywords: Carbon nanotubes; Pyrolysis; Transmission electron microscopy; Raman spectroscopy;

Acrylonitrile butadiene rubber (NBR) compounds filled with 40 phr of high abrasion furnace black (HAF) and HAF (20 phr)/graphite (20 phr) were experimentally investigated. The stress–strain curves of the composites were studied, which are described by applying Ogden's model. The effect of cyclic fatigue and hysteresis was also examined. The dissipation energy that indicates the vibration damping capacity for all samples was determined. A continuum damage model is used to investigate the fatigue damage behavior for elastomers. Experiments on the cyclic fatigue of a carbon-filled NBR rubber and carbon/graphite filled NBR rubber were conducted to determine the relation between the number of cyclic fatigue and the strain amplitude. The results indicate that the theoretical formula for the number of cyclic fatigue as a function of the strain amplitude, derived from the damage model, can describe experimental data for the prepared samples very well.
Keywords: Cyclic stress–strain; Graphite; Ogden model; Mahmoud model;

An analytical protocol was set up and successfully applied to study the food safety of recycled HDPE and PP crates. A worst-case scenario was applied that focused not only on overall migration and specific migration of accepted starting materials but also on migratable degradation products of polymers and additives that may be formed during mechanical recycling.The analytical protocol was set up to cover a wide variety of possible migrants. Identification and semi-quantification were possible for almost all migrants that increased significantly with increasing mechanical recycling steps for both the HDPE and PP crates.It was concluded that the analytical protocol was suitable to study the influence of (multiple) recycling on the food safety of plastic materials. The protocol can be applied to other plastic food contact materials and provides valuable information on the food safety of the recycling process and the resulting recycled food contact materials in addition to challenge testing.
Keywords: Recycling; High-density polyethylene; Polypropylene; Migration; Food safety; Degradation;

Metallocene and Ziegler–Natta (ZN) linear low density polyethylenes (LLDPEs) of different branch types and contents as well as linear high density polyethylene (HDPE) were exposed to natural and accelerated weather conditions. The degree of UV degradation of exposed samples was measured by rheological techniques and results were compared with unexposed polymers. Dynamic shear measurements were performed in an ARES rheometer in the linear viscoelastic range. The degree of enhancement or reduction in viscosity and elasticity was used as a measure of the degree of cross-linking or chain scission, respectively. The degradation results of LLDPE suggest that both cross-linking and chain scission are taking place. Chain scission dominated the degradation at high levels of short chain branching (SCB) and long exposure times. The degradation mechanism of m-LLDPE and ZN-LLDPE is similar; however, m-LLDPE showed a higher degradation rate than ZN-LLDPE of similar M w and average SCB. ZN-LLDPE was found to be more stable than a similar m-LLDPE. Comonomer type had little influence on degradation. Dynamic shear rheology was very useful in revealing the influence of different molecular parameters and it exposed the degradation mechanism.
Keywords: Degradation; Weathering; Molecular structure; Linear low density polyethylene; High density polyethylene; Cross-linking;

Central composite experimental design methods have been used to examine the simultaneous effects of talc (Viaton Viatalc® 30), titanium dioxide (modified Rutile, Tioxide® TR92) and additional hindered phenolic stabiliser (Aquanox® L, a 50% w/w aqueous dispersion of Winstay® L) on the water uptake and UV stability of composite films based on a carboxylated styrene butadiene rubber (c-SBR) latex. The talc and TR92 were in situ treated as pre-dispersions with Solsperse® S27000 and Solplus® D540 dispersants, respectively. For water uptake related responses, quadratic models were found to provide the most accurate prediction of effects associated with interactions between talc and TR92. It was found that the addition of TR92 to formulations with high talc loading reduced the water uptake, this was attributed a packing effect that arose due to the vast difference in pigment and filler particle size. For responses related to photo-oxidation (Microscal unit/mercury lamp, carboxylic acid carbonyl growth was monitored by IR), linear models gave the best data fit, thus indicating negligible interaction between the three variables. Within the experimental space explored, the level of talc had by far the strongest influence; increasing talc level led to a proportional increase in rate of carbonyl growth. This corroborates previous single variable studies, where the iron impurities present in the talc were suspected to be associated with the pro-degradant effect observed. Interestingly, the addition of dispersants amplified the latter effect and strongly muted the UV stabilising effect of TR92. An optimised formulation based on c-SBR was determined from the response equations and subsequently evaluated; in general the actual response trends matched those predicted. The suitability of experimental design as a tool to discover effects, interactions and responses of the ingredients of a paint system, and to optimise its formulation was thus confirmed.
Keywords: Latex; Water born paints; Experimental design; UV stability; Water uptake; Titanium dioxide;

Influence of water on the photodegradation of poly(ethylene oxide) by F. Hassouna; S. Morlat-Thérias; G. Mailhot; J.L. Gardette (2042-2050).
The UV-light degradation of polyethylene oxide (PEO) in aqueous solution was investigated operating under long wavelengths (λ  > 300 nm) at 20 °C in different pH conditions varying from 2.3 to 12.0 and at two different concentrations. Thermo-oxidation experiments on PEO aqueous solution at 50 °C are also reported and compared to photo-oxidation results. The formation of oxidation products was followed by infrared analysis of deposits obtained by evaporation of aliquots of irradiated polymer solution. Photo-oxidation led to formates and esters but a third product was also identified, formic acid ions formed by partial hydrolysis of formates. The degradation of PEO in water led to the acidification of the aquatic medium. Size exclusion chromatography (SEC) was used to monitor the changes in molar weight and intrinsic viscosity with irradiation time. It was shown that the photo-oxidation produced a dramatic decrease of the average molar weights which is more important in acidic medium. Total organic carbon (TOC) measurements of the aged aqueous solutions showed that the mineralization of PEO could not be achieved in these photo-oxidative conditions.
Keywords: Photodegradation; Water; Poly(ethylene oxide); SEC;

Thermal non-oxidative degradability of two epoxy thermosets was studied. Investigations were carried out on a non-commercial liquid crystalline structure and its isotropic homologue in order to provide further insight into the mechanism and kinetics of thermal degradation of the proposed systems. The studies were done by thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). For the first time the degradation of a liquid crystalline epoxy was studied using an advanced isoconversional kinetic method. The results were used to predict the thermal stability of both types of epoxy networks. GC–MS analysis was applied on evolved gas during degradation to elucidate the degradation mechanism in accordance with the kinetic results. The liquid crystalline structure has a different mechanism of decomposition in comparison with its isotropic homologue. In spite of a higher T g value, it shows a similar thermal stability but a lower release of degradation compounds.
Keywords: Degradation mechanism; Thermal stability; Liquid crystalline epoxy; Advanced isoconversional method; Kinetics;

Photodegradation studies of novel biodegradable blends based on poly(ethylene oxide) and pectin by Halina Kaczmarek; Krzysztof Bajer; Piotr Gałka; Barbara Kotnowska (2058-2069).
Blends of two biodegradable polymers: natural pectin and synthetic poly(ethylene oxide) at different weight-ratios were obtained by physical mixing in aqueous solutions, and evaporation of the solvent. The macromolecular order in the composites was investigated by applying X-ray diffraction, while the surface morphology was observed using atomic force microscopy. The photooxidative degradation of the blends was studied by viscometry, FTIR spectroscopy and UV–vis spectroscopy. It has been found that the susceptibility of the studied composites to UV radiation depends on an appropriate ratio of components, and the most sensitive to UV-irradiation among the samples studied was the equal weight-ratio blend of poly(ethylene oxide)/pectin.
Keywords: Pectin; Poly(ethylene oxide); Polymer blends; Photooxidative degradation;

Drag-induced apparent mass gain in thermogravimetry by R.J. Crewe; J.E.J. Staggs; P.T. Williams (2070-2075).
This paper shows how aerodynamic drag in thermogravimetric equipment may be corrected, and noise inherent in the data removed. Although it is entirely possible to correct drag-induced mass gain empirically, this publication is intended to allow the reader to understand the cause, correct for it, and remove noise appropriately. Apparent mass gain is described in terms of a generalised Stokes' formulation. A method is developed that enables the quantification of drag inside thermogravimetric equipment, which when combined with the Savitsky–Golay smoothing filter enables temperature-dependent apparent weight gain effects to be removed. It is necessary to account for this effect in proximate analysis and in the determination of kinetic parameters of thermal degradation.
Keywords: Thermogravimetry; TGA; TG; Buoyancy; Aerodynamic; Drag;

The origins of volatile oxidation products in the thermal degradation of polypropylene, identified by selective isotopic labeling by Robert Bernstein; Steven M. Thornberg; Roger A. Assink; Adriane N. Irwin; James M. Hochrein; Jason R. Brown; Dora K. Derzon; Sara B. Klamo; Roger L. Clough (2076-2094).
Making use of polypropylene samples that are selectively labeled with carbon-13 at each of the three unique positions within the repeating unit, we are conducting mass spectral analyses of the volatile organic oxidation products that are produced when the polymer is subjected to elevated temperature in the presence of air. By examination of both the parent and fragmentation ion peaks in the mass spectrum, we are able to identify the positioning of the C-13 labels within the volatile compounds, and thereby map each compound onto its site of origin from within the macromolecular structure of polypropylene. Most of the organic oxidation products are remarkably specific in terms of their genesis from the polymer. The structural results are discussed in terms of the oxidation chemistry of the macromolecule.
Keywords: Radiation degradation; Radiation oxidation; Polypropylene degradation; Polypropylene irradiation; Radiolysis products; Volatile degradation products;

Chain scission and crosslinking rates have been derived from molecular mass distributions obtained by gel permeation chromatography at different stages during photodegradation of polypropylene samples exposed to ultraviolet irradiation (UV). Results for rubber-toughened polypropylene (PP) containing no photostabilizer are compared with those for the same polymer stabilized using a commercial photostabilizing package (PPS). The samples were in the form of 3 mm thick bars and measurements were obtained at various depths from the exposed surface after different exposure times. The depth profiles for PP and PPS were very different. Reaction rates in the interior of PP showed oxygen diffusion limited behaviour and after prolonged exposure, the rates in the interior of PPS were higher than those in PP. The ratio of scission rate/crosslink rate fell when reaction rate increased. Crosslinking became relatively more likely when reaction rates were low. The low degradation rates obtained with stabilized polymer coupled with the sensitivity of the method of analysis enabled detection of inhibition of photodegradation attributed to residual moulding stresses in the samples.
Keywords: Polypropylene; Stabilizer; Photodegradation; Molecular weight distribution; Scission; Crosslinking;

Thin films of polypropylene were doped with a chemiluminescence (CL) activator, 9,10-diphenylanthracene (DPA), and were thermally oxidised in a CL imaging apparatus to determine whether heterogeneous oxidation processes such as spreading of oxidation could be observed. The presence of DPA resulted in significantly more intense CL images compared with undoped polymer, due to the efficient chemically induced electron exchange luminescence reaction between DPA and hydroperoxides. Hence, the CL images from DPA-doped PP were used to locate the position of hydroperoxides in the oxidising polymer. For thermal oxidation at 150 and 140 °C hydroperoxides were observed to form in localised regions of the films, whilst other areas remained hydroperoxide free. As the oxidation time increased the concentration of hydroperoxides in these areas increased and they were observed to spread to the remainder of the polymer. Time-resolved line maps from the images indicated that zones with high concentration of hydroperoxides travel through the polymer during oxidation. Integrals of CL images from the thermal oxidation of DPA-doped polymers indicated that a significant degree of oxidation had occurred by the end of the “induction period” for a conventional CL-intensity oxidation–time profile. This is a likely reason why spreading of oxidation has not previously been observed for undoped PP films.
Keywords: Chemiluminescence imaging; Chemically induced electron exchange luminescence; Polypropylene oxidation; 9,10-Diphenylanthracene; Heterogeneous oxidation; Oxidative spreading;

The effect of polishing time on measured oxidation thickness and elastic modulus of isothermally aged PMR-15 neat resin was investigated. A specimen aged 956 h in ambient air at 288 °C (550 °F) was selected for this study. Thermo-oxidation of the specimen results in a surface oxidation layer with different stiffness and polishing characteristics than the interior of the specimen. The specimen was repolished at consecutive time periods from a quick polishing time to extensive polishing time. A white light interferometer was used as a surface profiler to measure height variations from the specimen edges into the interior of the material. Subsequently, optical microscopy and nanoindentation experiments were conducted to correlate observations of oxidation thickness and elastic modulus measurements with polishing time. The modulus profiles obtained from nanoindentation experiments indicate formation of an outer brittle layer followed by a sharp drop in the transition region to the unoxidized interior. The oxidized material is polished at a greater rate than the unoxidized material. The maximum variation in the surface profile from polishing was limited to 5 μm across the oxidation layer (∼150 μm), which results in a slope of ∼2° over the oxidized region. Optical measurements of thickness of oxidized layer and transition region are in good agreement with the height and modulus profiles obtained using the interferometer and nanoindenter, respectively. Results from three techniques show that the measured oxidation thickness and elastic modulus are relatively independent of the polishing time.
Keywords: Nanoindentation; Modulus; Surface profile; Optical microscopy;

The experimental kinetics of decomposition of polyethylene hydroperoxides in the melt is re-examined. It is found that the rates determined are more accurate if only the “free” hydroperoxides are taken into account instead of the total hydroperoxides that include also the “associated” hydroperoxides. Then, decomposition of polyethylene hydroperoxides in the melt can be attributed unambiguously to a first-order reaction that is valid in the whole time range of the thermolysis experiments. Nevertheless, the first-order rate constant determined this way increases with the initial hydroperoxide concentration. This constitutes a significant difference with the first-order rate constants that are valid in low molecular mass chemistry and are independent of the initial concentration of the reacting species. It has already been concluded previously that this experimental first-order rate cannot be attributed to true monomolecular hydroperoxide decomposition. Hence, another or other reactions must be envisaged for the interpretation of the specific first-order decomposition of the hydroperoxides in polyethylene melts.
Keywords: Polyethylene; Melt; Thermolysis; Hydroperoxides; Kinetics;