Chemiluminescence spectral analysis of styrene-butadiene and acrylonitrile-butadiene rubbers using a multichannel Fourier-transform chemiluminescence spectrometer

The chemiluminescence spectra of styrene-butadiene and acrylonitrile-butadiene rubbers isothermally heated in the range between room temperature and 200 °C were measured with a multichannel Fourier-transform chemiluminescence spectrometer. The observed spectra were analyzed by a least-squares fit using a Gaussian function to determine the peak intensity and the peak wavelength of emission bands. It was found that the peak wavelength of acrylonitrile-butadiene rubbers was slightly longer than that of styrene-butadiene rubbers due to the influence of the nitrile groups. The peak intensity of chemiluminescence from styrene-butadiene rubbers decreased with the styrene content, while that from hydrogenated acrylonitrile-butadiene rubbers increased with the iodine value. From these experimental results, it is concluded that the content of double bonds in the butadiene units in rubbers is measurable by chemiluminescence spectral analysis.     

Thermal oxidative degradation kinetics of flame-retarded polypropylene with intumescent flame-retardant master batches in situ prepared in twin-screw extruder

The thermal oxidative degradation kinetics of pure PP and the flame-retarded (FR) PP materials with intumescent flame-retardant (IFR) master batches in situ prepared in twin-screw extruder were investigated using Kissinger method, Flynn-Wall-Ozawa method and Coats-Redfern method. The results showed that the activation energy order of PP and FR PP samples with different blowing agent/char former ratios obtained by Kissinger method agrees well with that obtained by Coats-Redfern one, which well illustrates the relationship between the composition of IFRs and their flame-retardancy, i.e. FR material with richer carbonization agent has higher activation energy for thermal oxidative degradation, hence leading to a better flame-retardancy. For Flynn-Wall-Ozawa method, due to its adoption of Doyle approximation, the obtained activation energy and its order of samples are very different from those of both Kissinger and Coats-Redfern methods. Criado method was finally used to determine the degradation reaction mechanism of various samples.     

Thermal degradation analysis and XRD characterisation of fibre-forming synthetic polypropylene containing nanoclay

Flammability of synthetic fibres is significantly worse than that of bulk polymers because of the high surface area to volume ratio and the low tolerance to high filler loadings in the fibre production process. Introducing nanocomposite structures has the potential to enhance the char formation at relatively low loadings of nanoparticulate fillers and hence can reduce the flammability of synthetic polymers and fibres.This paper reports thermal degradation analysis results in conjunction with TG analysis under different atmospheres and further studies of X-ray diffraction characterisation of fibre-forming polypropylene containing selected dispersed nanoclays.The concentrations of hydrocarbons, carbon monoxide and carbon dioxide released during the TG analysis have been monitored and analysed by using a combined electrochemical infrared analyser. The intensity changes of the crystallinity peaks and nanoclay peaks in the polymer and composites are discussed.     

Development of a novel potentiometric titration method for determination of polypropylene degradation

In this study, a novel potentiometric titration of hydroperoxide in degraded polypropylene (PP) is proposed. This titration is quite sensitive compared with the conventional ones such as UV and manual titrations, and its detection limit was about 2 meq/kg. The sensitivity was equal to that of molecular weight measurement by GPC for the degraded PP and, in addition, the volatilization behavior of the hydroperoxide could be detected. This titration was found to be very effective for the determination of PP degradation.     

Thermal degradation behaviors of a novel nanocomposite based on polypropylene and Co-Al layered double hydroxide

The thermal degradation behaviors of a novel nanocomposite based on polypropylene and organic Co/Al layered double hydroxide (PP/CoAl-LDH) were studied via thermogravimetric analysis (TGA) in the present work. The thermal degradation activation energies of the PP/CoAl-LDH nanocomposite were determined via Friedman and Flynn-Wall-Ozawa methods, and were compared with those of neat PP. The relationship between the organic CoAl-LDH concentration and the activation energies in PP/CoAl-LDH nanocomposite also has been investigated. An internal reason and an outer reason leading to high fire retardancy of PP/CoAl-LDH nanocomposite were proposed. The presence of CoAl-LDH tended to increase significantly the decomposition activation energy of nanocomposite at full-scale temperature and had an important influence on both of internal and outer reasons.     

Thermal oxidative degradation of poly-lactic acid

The study of molecular weight and rate of change of molecular weight during thermal degradation of PLA suggests the random nature of chain scission with activation energy of 28 kcal/mol. The rate of weight loss indicates the formation of the volatiles by chain end initiation. The melting temperature of the polymer initially decreases and afterwards increases with increase in time of heating due to chain stiffening.     

Use of 9,10-diphenylanthracene as a contrast agent in chemiluminescence imaging: The observation of spreading of oxidative degradation in thin polypropylene films

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.     

Sub-micron scale mechanical properties of polypropylene fibers exposed to ultraviolet and thermal degradation

Nanoindentation using atomic force microscopy (AFM) was conducted to investigate the affect of accelerated ultraviolet (UV) and thermal degradation on the mechanical properties of polypropylene fibers. The affect of degradation on Young’s modulus across fiber cross-sections was investigated with progressive nanoindentation from the surface to the center of the fiber. UV degradation initially increases the Young’s modulus both at the center and the surface of the fibers until 120 h of exposure with the increase being more rapid at the surface. Moduli started to decrease beyond 120 h of exposure. Wide angle x-ray scattering shows an increase of crystallinity up to 120 h of exposure and total destruction of crystallinity at 144 h. Infrared spectra showed the formation of carbonyl bonds with UV exposure. To investigate thermal degradation, the fibers were exposed to 125 °C for four weeks. Young’s modulus increased near the surface after four weeks exposure. These results support the idea that surface degradation may lead to embrittlement of textile fibers.     

Synergistic effect of nanoflaky manganese phosphate on thermal degradation and flame retardant properties of intumescent flame retardant polypropylene system

Nanoflaky manganese phosphate (NMP) was synthesized from manganese nitrate and trisodium phosphate dodecahydrate, and used as a synergistic agent on the flame retardancy of polypropylene (PP)/intumescent flame retardant (IFR) system. The thermogravimetric analysis (TGA), real time Fourier-transform infrared (RTFTIR) spectroscopy measurements, cone calorimeter (CONE) and microscale combustion calorimeter (MCC) were used to evaluate the synergistic effects of NMP on PP/IFR system. When IFR + NMP was fixed at 20 wt% in flame retardant PP system, the TGA tests showed that NMP could enhance the thermal stability of PP/IFR system at initial temperature from about room temperature to 440 °C and effectively increase the char residue formation. The RTFTIR results revealed that NMP could clearly change the decomposition behavior of PP in PP/IFR system, which promotes decomposition at the initial temperature from about room temperature to 260 °C and forms more effective barrier layer to protect PP from decomposing at high temperature from about 260 °C to 500 °C. The CONE tests indicated that the addition of NMP in PP/IFR system not only reduced the peak heat release rate (HRR), but also prolonged the ignition time. The MCC results revealed that PP/IFR/NMP system generated less combustion heat over the course of heating than that of PP/IFR system. And scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were used to explore the char residues of the PP/IFR systems with and without NMP.     

Kinetics of thermal degradation and estimation of lifetime for polypropylene particles: Effects of particle size

The thermal stability and degradation behavior of polypropylene (PP) particles having diameter varying from few micrometers to nanometers were studied by thermogravimetric analysis (TGA). The PP particles of average diameter ∼20 μm, ∼10 μm, ∼5 μm, ∼1 μm and <500 nm were studied over a range of temperature from 25 to 600 °C in N₂ atmosphere and heating rates of 5, 10 and 15 °C/min. Thermal stability of PP particles initially decreases and then increases as particle size further decreases to nanometer scale. The five single heating rate techniques such as Friedman, Freeman-Carroll, Chang, Coats-Redfern and second Kissinger; and three multiple heating rate techniques such as the first Kissinger, Kim-Park and Flynn-Wall were used to compute the kinetic parameters of degradation reaction, e.g., activation energy (E_a), order of reaction (n) and frequency factor [ln(Z)]. The lifetime of macro-, micro- and nanosized PP particles was also estimated by a method proposed by Toop. It was found that the activation energy and lifetime of nanosized PP particles are moderately high compared to the microsized PP particles. Moreover, the decomposition temperature, order of reaction (n), frequency factor [ln(Z)] not only depend on the heating rate and calculation technique but also on the particle size of polymer. The results are compared with macrosized PP.     

Kinetics of thermal degradation and thermal oxidative degradation of poly(p-dioxanone)

The kinetics of the thermal degradation and thermal oxidative degradation of poly(p-dioxanone) (PPDO) were investigated by thermogravimetric analysis. Kissinger method, Friedman method, Flynn-Wall-Ozawa method and Coats-Redfern method have been used to determine the activation energies of PPDO degradation. The results showed that the thermal stability of PPDO in pure nitrogen is higher than that in air atmosphere. The analyses of the solid-state processes mechanism of PPDO by Coats-Redfern method and Criado et al. method showed: the thermal degradation process of PPDO goes to a mechanism involving random nucleation with one nucleus on the individual particle (F₁ mechanism); otherwise, the thermal oxidative degradation process of PPDO is corresponding to a nucleation and growth mechanism (A₂ mechanism).     

Gel production, oxidative degradation and dielectric properties of isotactic polypropylene irradiated under various atmospheres

In this work, changes in structure and physical properties of stabilized isotactic polypropylene (iPP) were created by gamma irradiation, up to a dose of 700 kGy, in different media: air, deionised distilled (DD) water and acetylene. Gel and infrared (IR) spectroscopy measurements were used to determine the changes in the degree of network formation and oxidative degradation, respectively. Sol-gel analysis was studied in detail using the Charlesby-Pinner (C-P) equation. The radiation-induced changes in the structure and evolution of oxygen-containing species were also studied through dielectric loss (tan δ) analysis in a wide temperature and/or frequency range. Evolution of low temperature dielectric relaxations with gamma irradiation was investigated. In the case of dielectric relaxation measurements, the polar groups that were introduced by irradiation in non-polar iPP were considered as tracer groups. Conclusions derived according to different methods were compared.     

Thermal stability and degradation products analysis of benzocyclobutene-terminated imide polymers

Benzocyclobutene-terminated imides were prepared and fully characterized with ¹H NMR, MS, and FT-IR. The thermal degradation of polymers was investigated by using thermogravimetric analyzer (TGA) and high-resolution pyrolysis-gas chromatography–mass spectrometry (HR-Py-GC–MS). TGA showed that thermal degradation of the polymer was a single-stage process in N₂, whereas a three-stage degradation in air atmosphere. The major involved products were found to be CO₂, naphthalene and naphthalene derivatives. Degradation mechanism of the polymer was suggested and the relationship between structures of the polymer and degradation products was also discussed.     

The origins of volatile oxidation products in the thermal degradation of polypropylene, identified by selective isotopic labeling

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.     

Effect of a novel charring-foaming agent on flame retardancy and thermal degradation of intumescent flame retardant polypropylene

A new triazine polymer was synthesized by using cyanuric chloride, ethanolamine and ethylenediamine as raw materials. It is used both as a charring agent and as a foaming agent in intumescent flame retardants, designated as charring-foaming agent (CFA). Effect of CFA on flame retardancy, thermal degradation and mechanical properties of intumescent flame retardant polypropylene (PP) system (IFR-PP system) has been investigated. The results demonstrated that the intumescent flame retardant (IFR) consisting of CFA, APP and Zeolite 4A is very effective in flame retardancy of PP. It was found that when the weight ratio of CFA to APP is 1:2, that is, the components of the IFR are 64 wt% APP, 32 wt% CFA and 4 wt% Zeolite 4A, the IFR presents the most effective flame retardancy in PP systems. LOI value of IFR-PP reaches 37.0, when the IFR loading is 25 wt% in PP. It was also found that when the IFR loading is only 18 wt% in PP, the flame retardancy of IFR-PP can still pass V-0 rating, and its LOI value reaches 30.2. TGA data obtained in pure nitrogen demonstrated that CFA has a good ability of char formation itself, and CFA shows a high initial temperature of the thermal degradation. The char residue of CFA can reach 35.7 wt% at 700 °C. APP could effectively promote the char formation of the APP-CFA system. The char residue reaches 39.7 wt% at 700 °C, while it is 19.5% based on calculation. The IFR can change the thermal degradation behaviour of PP, enhance T_max of the decomposition peak of PP, and promote PP to form char, based upon the results of the calculation and the experiment. This is attributed to the fact that endothermic reactions took place in IFR charring process and the char layer formed by IFR prevented heat from transferring into inside of IFR-PP system. TGA results further explained the effective flame retardancy of the IFR containing CFA.     

Thermal degradation behaviour of aromatic poly(ester-amide) with pendant phosphorus groups investigated by pyrolysis-GC/MS

The thermal stability of a novel phosphorus-containing aromatic poly(ester-amide) ODOP-PEA was investigated by thermogravimetric analysis (TGA). The weight of ODOP-PEA fell slightly at the temperature range of 300-400 °C in the TGA analysis, and the major weight loss occurred at 500 °C. The structural identification of the volatile products resulted from the ODOP-PEA pyrolysis at different temperatures was performed by pyrolysis-gas chromatography/mass spectrometry (pyrolysis-GC/MS). The P-C bond linked between the pendant DOPO group and the polymer chain disconnected first at approximately 275 °C, indicating that it is the weakest bond in the ODOP-PEA. The P-O bond in the pendant DOPO group was stable up to 300 °C. The cleavage of the ester linkage within the polymer main chain initiated at 400 °C, and the amide bond scission occurred at greater than 400 °C. The structures of the decomposition products were used to propose the degradation processes happening during the pyrolysis of the polymer.     

The genesis of CO2 and CO in the thermooxidative degradation of polypropylene

Using a set of three isotactic polypropylene samples that had been individually labeled with carbon-13 at each of the three positions in the monomer unit, we conducted experiments to determine the position of origin of carbon monoxide and carbon dioxide that arise during thermal oxidation of this polymer. By GC-mass-spectral analysis, we find that 2/3 of the CO₂ derives from the C(1) [methylene] carbon and the remaining 1/3 comes from the C(2) [tertiary] carbon, with none coming from the C(3) [methyl group] carbon. The CO also comes mainly from the C(1) [methylene] carbon (≥80%). This is in contrast to the solid-phase oxidation products, which have been found (by C-13 NMR on these same labeled PP materials) to originate predominantly (80-85%) from oxidation at the C(2) [tertiary] carbon. These results can be understood in terms of the free-radical reactions that underlie the polypropylene oxidation chemistry.     

The effect of adding virgin material or extra stabilizer on the recyclability of polypropylene as studied by multi-cell imaging chemiluminescence and microcalorimetry

The effect of adding virgin material or new stabilizers on the recyclability of polypropylene (PP) was determined. Stabilized PP was subjected to oven ageing at 130 °C for 100, 250 or 500 h before and after upgrading with virgin material (0, 20, 50, 80 or 100%) or additional stabilizer during reprocessing. The effect of upgrading recycled PP with extra stabilizer or virgin material was determined by measuring the elongation at break, yellowness change, oxidation induction time (OIT) or total luminous intensity (TLI) by chemiluminescence (CL) techniques. Selected specimens were analysed by microcalorimetry (MC).It has been shown that upgrading recycled PP with virgin material was not effective. Adding 80% virgin material did not increase the lifetime more than adding 20% virgin material. This indicates that a small amount of recycled material can induce degradation by contamination. Adding extra stabilizers instead of virgin material was much more effective. Of all techniques used the OIT as determined with CL showed a clear difference in residual stability of differently treated materials and seems to be the most valuable analytical method to determine the recyclability of PP. A comparison between CL and MC shows that MC is sensitive enough for measuring the solid-state oxidation of stabilized PP. Slightly lower OITs were detected by MC probably associated with the static atmosphere used during the measurements. The TLI method is not suitable to determine the degradation state of to be recycled material.     

Flammability and thermal degradation of flame retarded polypropylene composites containing melamine phosphate and pentaerythritol derivatives

The flammability of polypropylene (PP) composites containing intumescent flame retardant additives, i.e. melamine phosphate (MP) and pentaerythritol (PER), dipentaerythritol (DPER) or tripentaerythritol (TPER) was characterized by limiting oxygen index (LOI), UL 94 and the cone calorimeter, and the thermal degradation of the composites was studied using thermogravimetric analysis (TG) and real time Fourier transform infrared (RTFTIR). It has been found that the PP composite containing only MP does not show good flame retardancy even at 40% additive level. Compared with the PP/MP binary composite, the LOI values of the PP/MP/PER (PP/MP/DPER or PP/MP/TPER) ternary composites at the same additive loading are all increased, and UL 94 ratings of most ternary composites studied are raised to V-0 from no rating (PP/MP). The cone calorimeter results show that the heat release rate and smoke emission of some ternary composites decrease in comparison with the binary composite. It is noted from the TG data that initial decomposition temperatures of ternary composites are lower than that of the binary composite. The RTFTIR study indicates that the PP/IFR composites have higher thermal oxidative stability than the pure PP.     

Emission of possible odourous low molecular weight compounds in recycled biofibre/polypropylene composites monitored by head-space SPME-GC–MS

A disadvantage of the use of natural fibres to reinforce polypropylene is their poor thermal stability, which results in their degradation at processing temperatures of the composites. As a result of this, there is a formation of low molecular weight compounds that are responsible for undesirable odours. Head-space-solid phase microextraction (HS-SPME) was used as a sample preparation technique and gas chromatography–mass spectrometry (GC–MS) was used to identify the low molecular weight compounds in natural polypropylene/polypropylene composites after simulating degradation. Among the compounds found in the samples, there are fragments of PP chains as heptadecane, compounds from antioxidants such as 2,4-bis(1,1-dimethylethyl)-phenol, and p-tert-butylphenol, and compounds from biofibres ageing, such as ethylparaben and vanillin. Numerous carboxylic acids were also identified, being these most probably the source of the undesirable odours.