Polymer Degradation and Stability (v.94, #5)

Calendar (I-II).

The synergistic effects and mechanism of multiwalled carbon nanotubes (MWNTs) with magnesium hydroxide (MH) in halogen-free flame retardant EVA/MH/MWNT nanocomposites have been studied by cone calorimeter test (CCT), limiting oxygen index (LOI), thermogravimetric analysis (TGA), torque test, morphological evolution experiment, and scanning electron microscopy (SEM). The data obtained from the CCT, LOI, and TGA show that suitable amount of MWNTs has synergistic effects with MH in the EVA/MH/MWNT nanocomposites. The MWNTs can considerably decrease the heat release rates and mass loss rate by about 50–60%, prolongate the combustion time to near two times, and increase the LOI values by 5% when 2 wt% MWNTs substitute for the MH in the EVA/MH/MWNT samples. The TGA data also show that the synergistic effects of MWNTs with MH apparently increase the thermal degradation temperatures and final charred residues of the EVA/MH/MWNT samples. The experimental observations from the torque, morphological evolution tests, and SEM give positive evidences that the synergistic mechanism of MWNTs with MH can be described to: (i) the increase of melt viscosity because of network structure formation of MWNTs in the EVA/MH matrix; (ii) the enhancement of thermo-oxidation stability due to the MWNTs' mechanical strength and integrity of the charred layers in the EVA/MH/MWNT nanocomposites; (iii) the formation of compact charred layers promoted by MWNTs acted as heat barrier and thermal insulation. All the above-mentioned factors efficiently enhance thermal and flame retardant properties and protect the EVA/MH/MWNT nanocomposite materials to be burning.
Keywords: Ethylene-vinyl acetate copolymer; Multiwalled carbon nanotubes; Magnesium hydroxide; Synergistic effect; Halogen-free flame retardant;

Characterisation of flavour compounds formed by γ-irradiation of polypropylene by Oxana Tyapkova; Michael Czerny; Andrea Buettner (757-769).
Sterilisation of plastic packaging materials for food, pharmaceutical or cosmetic products with 60Co γ-irradiation in the presence of oxygen can result in the formation of volatile substances. These may subsequently induce off-odours in these materials that might be regarded as negative by the consumers. Trace volatiles and odorous substances of polypropylene, irradiated with 60Co γ rays at 10 and 20 kGy, respectively, were collected and analysed by gas chromatography–olfactometry (GC–O), GC–MS and GC–GC–MS. The methodology was successfully applied for identification of 29 characteristic odorants in a non-irradiated control sample and 38 odorants in γ-irradiated polypropylene samples. Selected odour-active compounds were quantified using GC–GC–MS in combination with stable isotope dilution assays. The quantitative data mirrors the compositional changes in volatile odorous substances from polypropylene during treatment with ionising γ rays in a 60Co-irradiation plant.
Keywords: Aroma extract dilution analysis (AEDA); Gas chromatography–olfactometry (GC–O); Polypropylene (PP); γ-Irradiation; Radiolysis products;

Variation of anions in layered double hydroxides: Effects on dispersion and fire properties by Linjiang Wang; Shengpei Su; Dan Chen; Charles A. Wilkie (770-781).
Layered double hydroxides (LDHs) are interesting materials for nanocomposite formation because one can vary the identity of the metals, the anions and the stoichiometry to see the effect of these on the ability of the nano-material to disperse in a polymer and to see what effect dispersion has on the properties of the polymer. In this study, the anions 2-ethylhexyl sulfate (SEHS), bis(2-ethylhexyl) phosphate (HDEHP) and dodecyl benzenesulfonate (SDBS) have been utilized as the charge balancing anions to synthesize organo-LDHs. Nanocomposites of poly(methyl methacrylate) (PMMA) and polystyrene (PS) with organo-LDHs were prepared both by melt blending and bulk polymerization. X-ray diffraction and transmission electron microscopy were used to characterize the morphology of the nanocomposites while the thermal stability and fire properties of nanocomposites were studied by thermogravimetric analysis and cone calorimetry; the mechanical properties are also investigated. In general, it is easier to disperse these organo-LDHs in PMMA than in PS, but the sulfate cannot be dispersed at the nanometer level in either material. The addition of these organo-LDHs does not affect the mechanical properties. The best fire properties are obtained with the sulfonate LDH, SDBS; the reduction in the peak heat release rate is almost 50% for both polymers.
Keywords: Anions; Dispersion; Flame retardance; Poly(methyl methacrylate); Polystyrene; LDH nanocomposite;

Polyethylene (PE) was modified by the addition of a layered double hydroxide of zinc aluminum oleate (ZnAl) and/or commercial fire retardants. Commercial additives included: melamine polyphosphate (MPP), ammonium polyphosphate (APP), triphenol phosphate (TPP), resorcinol diphosphate (RDP), decabromophenyl oxide (DECA) and antimony oxide (AO). The thermal stability and the combustion behaviors of the new composite polymeric materials are evaluated in TGA experiments and cone calorimetry. At 20% total additive loading, APP and LDH enhance the thermal stability of the PE composites and favor char formation. ZnAl leads to the best reduction in the peak of heat release rate (PHRR), 72%, while the combinations of PE with other additives give reductions in the range 20–40%. The combination of DECA and AO effectively increases the time to ignition and time to PHRR while LDH lowers these two parameters. APP and MPP on the other hand, do not affect the time to ignition, but they effectively increase the time to PHRR relative to the pristine polymer.
Keywords: Polyethylene; Synergy; Fire retardancy; Nanocomposite; Phosphate fire retardants; Halogen-based fire retardants;

Effect of clay organomodifiers on degradation of polyhydroxyalkanoates by Perrine Bordes; Elodie Hablot; Eric Pollet; Luc Avérous (789-796).
Ammonium surfactants are commonly used as clay organomodifiers in nanocomposites. Their effect on the thermal- and thermo-mechanical degradation of polyhydroxyalkanoates (PHAs) is reported. Two poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) grades were tested and compared to polyhydroxybutyrate (PHB). Thermal stabilities were determined from thermogravimetric data and determination of molecular weight changes after processing was performed. The data revealed that all surfactants enhance the PHBV degradation. The results also highlight the preponderant effect of the initial M w rather than the HV content on the thermal stability. The thermo-mechanical study confirmed the role of surfactants and their different behaviour towards PHBV degradation. This study demonstrates that all surfactants enhance the PHA degradation since their decomposition products most likely act as catalytic agents.
Keywords: Ammonium surfactants; Biopolymers; Polyhydroxyalkanoates; Renewable resources; Thermal degradation;

Mechanism of intumescence of a polyethylene/calcium carbonate/stearic acid system by S. Bellayer; E. Tavard; S. Duquesne; A. Piechaczyk; S. Bourbigot (797-803).
In this work, we have investigated the intumescent behaviour of linear low-density polyethylene (LLDPE) containing calcium carbonate (chalk) treated by stearic acid. This system swells during burning and creates a protective layer when exposed to an external heat flux of 50 kW/m2 in a mass loss calorimeter. This system has been fully characterized by FTIR, XRD, TGA and SEM. The carbonation/decarbonation temperatures, the swelling phenomenon and the effect of the thermal stress on the swelling have been examined. The residue is composed of a smooth surface made of chalk and CaO and a bulk of only chalk. Stearic acid allows a good dispersion of chalk particles into the LLDPE matrix, and contributes to form a cohesive network during burning when the thermal stress is high enough. A governing parameter of the intumescent effect is the particle size, which permits the formation of an insulating and cohesive mineral network during burning.
Keywords: Polyethylene; Carbonate; Intumescence; Flame retardant;

Nanocomposites based on layered double hydroxides (LDH) and poly(p-dioxanone) (PPDO) were prepared by melt processing using dodecylbenzene sulfonate (DBS) and 4-hydroxybenzene sulfonate (HBS) as organic modifiers. The incorporation of organic anions in LDH was demonstrated by wide-angle X-ray scattering (WAXS) and Fourier transform infrared (FTIR). The dispersion degree of the organically modified LDHs in the PPDO matrix was analyzed by WAXS, indicating that only the LDH modified with HBS was exfoliated. The effect of the organically modified LDHs on the thermal stability of PPDO was studied using thermogravimetric analysis (TGA). The thermal stability of PPDO matrix was enhanced by the incorporation of the LDH modified with HBS due to the shielding effect of the exfoliated layers. In contrast, the LDH modified with DBS produced a decrease of the thermal stability of PPDO, probably due to hydrolytic decomposition of ester group. The thermogravimetric analysis also showed that the organo-modified LDH did not modify the thermal decomposition mechanism of the polymer, but had an effect on the thermal stability.
Keywords: Poly(p-dioxanone); Layered double hydroxides (LDHs); Nanocomposites; Thermal decomposition;

A detailed, mechanistic model for high-density polyethylene pyrolysis was created based on the modeling framework developed in our previous work and was used to study the time evolution of low molecular weight products formed. Specifically, the role that unzipping, backbiting, and random scission reaction pathways play in the evolution of low molecular weight species was probed. The model tracked 151 species and included over 11,000 reactions. Rate parameters were adapted from our previous work, literature values, and regression against experimental data. The model results were found to be in excellent agreement with experimental data for the evolution of condensable low molecular weight products. The time evolution curves of specific low molecular weight products indicated that the random scission pathway was important for all species, while the backbiting pathway played a complementary role. Net rate analysis was used to further elucidate the competition between the pathways. Net rate analysis of end-chain radicals showed that the unzipping pathway was not competitive with the other pathways, as expected based on experimental yields of ethylene. The random scission pathway was found to be controlling, with the backbiting pathway playing a more minor role for product formation. By comparing the net rates for formation of specific mid-chain radicals via intramolecular hydrogen shift reactions, the contribution of the backbiting pathway was shown to vary, with radicals formed via the most facile x,x  + 4-intramolecular hydrogen transfer reactions being favored.
Keywords: Pyrolysis; Mechanistic modeling; High-density; polyethylene; Kinetic modeling; Method of moments;

High efficiency voltage stabilizers for XLPE cable insulation by V. Englund; R. Huuva; S.M. Gubanski; T. Hjertberg (823-833).
A set of new voltage stabilizers has been synthesized, tested and has shown to suppress a degradation mechanism, i.e. electrical treeing, present in cross-linked polyethylene used for high-voltage cables. Electrical treeing is seen at very high and divergent electrical fields and has a rapid lapse from initiation to total breakdown of the insulation material. The new voltage stabilizers presented in this paper have increased the electrical tree inception field with up to 50% at such low additions as 0.4%-wt. Furthermore, the best-performing materials have also proven to increase the threshold level for tree inception, i.e. before this level no deterioration of the material is seen, up to 50%.
Keywords: Polyethylene; Electrical degradation; XLPE; Voltage stabilizer; Electrical treeing;

In this overview study, two ionic liquids (IL) with different anions (decanoate, tetrafluoroborate) but with the same phosphonium-based cation that showed promising plasticizing/lubricating behavior in polylactic acid (PLA) were screened for their effects on the polymer degradation under thermomechanical, thermo-oxidative (at 160 °C), hydrolytic (100% humidity, 60 °C), conditions, and during soil immersion. Depending on the particular medium and conditions used, degradation was followed by changes in molecular weight, melt viscosity, sample weight and appearance, morphology, crystallinity, acid number, and pH. The effects of the IL containing a decanoate anion were more pronounced on lubrication and also on degradation as evidenced by reduced melt viscosities and accelerated thermomechanical, isothermal, hydrolytic, and soil degradation. The IL containing the tetrafluoroborate anion showed higher thermal stability compared with the IL containing decanoate anion as also confirmed from thermal degradation rate constants which were calculated from random chain scission statistics. Accelerated hydrolytic degradation was observed in PLA containing the tetrafluoroborate based IL but to a lesser extent than the decanoate based IL. The catalytic role of the decanoate anion in hydrolytic degradation was confirmed through experiments with model compounds. X-ray diffraction (XRD) data on the materials exposed to soil degradation provided evidence that the initially amorphous polymer attained a certain degree of crystallinity as a result of the significant MW reduction.
Keywords: Ionic liquids; Polylactic acid; Thermal/hydrolytic degradation; Additives;

Influence of lanthanum stearate (LaSt3) as a co-stabilizer on stabilization efficiency of calcium stearate (Ca)/zinc glutarate (Zn) stabilizers to polyvinyl chloride (PVC) at 180 °C in air was investigated. The results showed that combination of LaSt3 with Ca/Zn stabilizers presented an obvious improvement of stabilization efficiency to PVC compared with the Ca/Zn stabilizers. Moreover, addition of LaSt3 to the Ca/Zn stabilizers could significantly enhance static stability time of PVC. Incorporation of 2 phr LaSt3 co-stabilizer to PVC containing 3 phr Ca/Zn stabilizers resulted in marked increase of onset degradation temperature and reductions in average degradation rate as well as the dynamic storage modulus (G′) and loss modulus (G″) at 180 °C. Influence of Ca/Zn ratio on tensile strength of PVC in the absence or in the presence of LaSt3 was discussed in detail. At low Ca/Zn ratios LaSt3 had an obvious improvement in the tensile strength, while at high Ca/Zn ratios this effect became inconspicuous.
Keywords: Polyvinyl chloride (PVC); Calcium/zinc stabilizers; Lanthanum stearate; Co-stabilizer;

In the present paper, the depolymerization of chitosan was carried out by the ultraviolet-irradiated oxygen treatment. Influence of reaction conditions on depolymerization of chitosan was investigated. The chemical structure of the depolymerized chitosan was characterized by FT-IR and 13C NMR spectra. The FT-IR and 13C NMR spectra suggested that there was no obvious modification of chemical structure of the depolymerized chitosan. The X-ray diffraction analysis showed that crystalline structure of chitosan can be destroyed by ultraviolet-irradiated oxygen. The use of depolymerization of chitosan by ultraviolet-irradiated oxygen treatment can be a convenient, timesaving, and cost-efficient method for replacing the expensive and time-consuming enzymatic or chemical methods that are currently used to depolymerize chitosan.
Keywords: Extremely high purity silica glass; Ultraviolet-irradiated oxygen; Depolymerization; Chitosan;

Experimental and theoretical investigation of stress corrosion crack (SCC) growth of polyethylene pipes by Byoung-Ho Choi; Alexander Chudnovsky; Rajesh Paradkar; William Michie; Zhenwen Zhou; Pak-Meng Cham (859-867).
Degradation of polymers is usually manifested in a reduction of molecular weight, increase of crystallinity in semicrystalline polymers, increase of material density, a subtle increase in yield strength, and a dramatic reduction in toughness. Stress corrosion cracking (SCC) results from strongly coupled thermo-mechano-chemical processes, and is sensitive to material composition and morphology. The individual crack propagation stage is critical in determining the lifetime of pipe. Based on author's previous works, crack layer (CL) theory model is adopted in this study to describe the individual stress corrosion (SC) crack propagation kinetics and the time interval from crack initiation to instability and break through. The effect of localized chemical degradation at the crack tip on SC crack growth kinetics is addressed. Typical SC crack growth is presented and discussed as a step-wise manner based on the proposed model. In addition, scanning electron microscopy (SEM) observation and Fourier transform Infrared spectroscopy (FTIR) analysis of failed samples obtained by accelerated SCC tests are applied to validate the proposed model. SEM is useful to identify the change of fracture mechanisms from chemically driven crack to mechanically driven crack by the formation of visible striations. FTIR analysis enables tracking of the accumulation of chemical degradation by detecting the amount of carbonyls on the crack surface. Carbonyl index is defined to compare the amount of chemical degradation quantitatively. The purpose of this paper is to continue to develop the technical theory and understanding behind SCC phenomena to facilitate all polymer pipe industries and in particular the polyethylene pipe industry to design better resins and piping systems.
Keywords: Stress corrosion crack; Fracture initiation; Crack propagation; Crack layer theory; SEM; FTIR;

New polymer–clay nanocomposites composed of poly(lactic acid) and a novel organoclay based on cocamidopropylbetaine (CAB) and sodium montmorillonite (MMT) were prepared by solution casting and characterised by X-Ray Diffraction Analysis (XRDA), Transmission Electron Microscopy (TEM) and Thermogravimetric Analysis (TGA). A similar series of composites based on PLA and Cloisite 30B, a commercially available organoclay, were prepared for comparison. The thermal stability of the CAB–MMT organoclays decreased with increasing surfactant loading. Experimental organoclays with an organic content similar to that of the commercial organoclay were found to be of comparable thermal stability. XRDA analysis of the PLA–organoclay nanocomposites showed that PLA intercalated the gallery space of both types of organoclay to similar extents and the increased spacing was confirmed by TEM. The thermal stabilities of the PLA–organoclay composites based on CAB–MMT were higher than those based on the commercial organoclay.
Keywords: Organoclay; Poly(lactic acid); Nanocomposite; Thermal stability; Biopolymer; Poly(lactic acid);

There is a growing interest in the development of nanocomposites consisting of organic polymers and TiO2 or amorphous SiO2 nanoparticles. These nanoparticles may be released from nanocomposites. There is evidence that amorphous SiO2 and TiO2 nanoparticles can be hazardous. Thus, in the design of nanocomposites with such nanoparticles, hazard reduction extending to the full nanocomposite life cycle would seem a matter to consider. Options for hazard reduction include: changes of nanoparticle surface, structure or composition, better fixation of nanoparticles in nanocomposites, including persistent suppression of oxidative damage to polymers by nanoparticles, and design changes leading to the release of relatively large particles.
Keywords: Nanocomposites; Amorphous SiO2; TiO2; Nanoparticles; Polymer; Hazard;