Flame retarding mechanism of polycarbonate containing methylphenyl-silicone

The thermal degradation of polycarbonate (PC) containing methylphenyl-silicone with a branched structure (SFR-PC) was investigated by the thermogravimetric analysis (TGA). The decomposition activation energies were determined using the Ozawa method. It was found that the decomposition activation energy and the degradation residue of the SFR-PC at 800 °C in air atmosphere were much higher than those of the PC. The addition of methylphenyl-silicone enhanced the thermal stability of PC and promoted the formation of char. The silicone was found effective in retarding the combustion of the PC. The limited oxygen index of the PC containing 5 wt.% of methylphenyl-silicone was 34%. Surfaces of the SFR-PC before and after combustion were analyzed by energy dispersive X-ray analysis (EDX) and infrared (IR) spectroscopy. Based on these results obtained, the flame retarding mechanism of the SFR-PC was discussed.     

TGA/FTIR study on thermal degradation of polymethacrylates containing carboxylic groups

In this work, the thermal degradation of polymethacrylates containing carboxylic groups namely poly(methacryloyloxy butanoic acid), PMBA; poly(methacryloyloxy hexanoic acid), PMHA; and poly(p-methacryloyloxy benzoic acid), PMBeA was investigated by TGA/FTIR. Moreover, in order to shed more light on the reaction pathways during the thermal decomposition of these polymers, an FTIR spectroscopic study of structural changes in the degrading material was performed. By TGA it was observed that PMBA exhibited two well-defined degradation stages at 327 and 450 °C; PMHA presents only one main weight loss at ca. 402 °C although from DTG curve it was noted that the single step degradation was composed by two overlapped peaks located at 414 and 449 °C and a small shoulder at 317 °C; finally PMBeA showed three weight loss regions at 265, 353 and 468 °C. From FTIR analysis of the partially degraded samples it was found that the thermal degradation of these polymers resembled that of polymethacrylic acid, i.e. anhydrides were initially formed and then the modified structure is broken to yield an aromatic structure with phenolic groups. In contrast, the analysis by FTIR of the volatile products from the studied polymers differs notably than those obtained for polymethacrylic acid: β-lactones and γ-lactones were released from PMBA and PMHA, respectively, during its thermal degradation, whereas an ester derivative from benzoic acid evolves from PMBeA probably through depolymerization.     

Effects of organoclay modifiers on the flammability, thermal and mechanical properties of polycarbonate nanocomposites filled with a phosphate and organoclays

Polycarbonate was melt blended with solid bisphenol A bis(diphenyl phosphate), and a series of organoclays. Effects of the organoclay modifiers on the flammability, thermal and mechanical properties of the nanocomposites were studied by limiting oxygen index, UL-94 burning test, thermogravimetric analysis, differential scanning calorimetry, tensile test and dynamic mechanical analysis. Although all the nanocomposites exhibit an intercalated-exfoliated morphology, they vary in the magnitude of intercalation revealed by X-ray diffraction and transmission electron microscopy. Flammability of the nanocomposites is strongly related to the thermal stability rather than the morphology. Glass transition temperature (T_g) and mechanical properties are controlled by both the morphology and the affinity of the organoclays with the matrix. The modifier containing hydroxyl moiety has stronger interactions with the matrix but it can promote its degradation, thus the corresponding nanocomposite exhibits a better intercalated morphology, higher T_g, superior strength and modulus however a worse thermal stability and flame retardancy. An additional silane within the organoclays would make the organoclays more compatible with the matrix but be a steric obstacle to the intercalation of the matrix chains; however, flame retardancy of the corresponding nanocomposite is enhanced due to the flame retardant nature of the silane. Similarly, the modifier bearing two long alkyl tails shows stronger affinity with the matrix than the one bearing a single tail, but it would hinder the intercalation due to the steric effect. These establishments between organoclay modifiers and the properties of nanocomposites might be guidance for developing materials with practical applications.     

Pyrolysis products and thermal degradation mechanism of intrinsically flame-retardant calcium alginate fibre

Intrinsically flame-retardant calcium alginate fibre was prepared by wet spinning and its pyrolysis products and thermal degradation mechanism studied. Combustion behaviour and flammability were assessed using the limiting oxygen index (LOI) and cone calorimetry. LOI results showed that calcium alginate fibre was intrinsically flame retardant with LOI value of 48.0, as compared to about 20.0 for viscose fibre. Cone calorimetry indicated that heat release rate and total heat release values of intrinsically flame-retardant fibre were significantly less than those of viscose fibre. It also shown that intrinsically flame-retardant fibre combustion produced greater quantities of residues than did viscose fibre combustion. Combustion residues were examined using scanning electron microscopy, indicating that calcium alginate fibre produced consistent, thick residue crusts. Pyrolysis was investigated using pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) which showed that cracking products produced from calcium alginate fibres combustion were less than those in viscose fibre combustion, and pyrolysis of the intrinsically flame-retardant fibre was incomplete. Thermogravimetric analysis (TG) indicated that calcium alginate fibre generated more residues containing carbonaceous char and calcium carbonate, as compared with viscose fibre. We propose a condensed phase mechanism for the calcium alginate fibre flame-retardancy effect.     

Thermal and thermo-oxidative degradation of poly(hydroxy ether of bisphenol-A) studied by TGA/FTIR and TGA/MS

The nature and the extent of degradation of poly(hydroxy ether of bisphenol-A) phenoxy resin were analysed by thermogravimetry (TGA/DTGA) under nitrogen and air atmosphere. Decomposition kinetics were elucidated according to Flynn-Wall-Ozawa, Friedman and Kissinger methods. The evolved gases during degradation were inspected by a thermogravimetry analyser coupled with Fourier Transform Infrared Spectrometer (TGA/FTIR) and also with a TGA coupled to a Mass Spectrometer (TGA/MS). Mass spectra showed that chemical species evolved in phenoxy decomposition in air were very similar to those assigned from degradation in nitrogen (water, methane, CO, CO₂, phenol, acetone, etc.). However, these species appear in different amount and at different temperatures in both atmospheres. FTIR analysis of the evolved products showed that water and methane were the beginning decomposition products, indicating that decomposition is initiated by dehydration and cleavage of C-CH₃ bond in the bisphenol-A unit of phenoxy resin. After this initial stage, random chain scission is the main degradation pathway. Nevertheless, in air atmosphere, previously the complete decomposition of the phenoxy obtaining fundamentally CO₂, and water, the formation of an insulated surface layer of crosslinked structures has been proposed.     

Effects of temperature on the weathering lifetime of coated polycarbonate

The lifetime of polycarbonate (PC) coated with silicone hardcoats containing UV absorber is shorter at elevated temperatures. The activation energy (E_a) for delamination was found to be 18 ± 2 kJ/mol (4.3 ± 0.5 kcal/mol) at the 95% confidence level in this study. This E_a is the consequence of the sensitivity of the substrate and the UV absorber to temperature. The E_a for PC photodegradation was previously found to be 17-21 kJ/mol (4-5 kcal/mol). The E_a for loss of absorbance in the second-generation silicone hardcoat was found to be 28.5 ± 5.4 kJ/mol (6.8 ± 1.3 kcal/mol) at the 95% confidence level. Results are consistent with experimental findings when these activation energies are used in published predictive models. Since the E_a for coating delamination depends on the E_a of UV absorber loss, coating systems different from the one in this study will need to be investigated separately.     

Effect of boron containing materials on flammability and thermal degradation of polyamide‐6 composites containing melamine cyanurate

Three different boron containing materials, zinc borate (ZnB), borophosphate (BPO₄), and boron and silicon containing oligomer (BSi), were used to improve the flame retardancy of melamine cyanurate (MC) in a polyamide‐6 (PA‐6) matrix. The combustion and thermal degradation characteristics were investigated using limiting oxygen index (LOI), UL‐94 standard, thermogravimetric analysis‐Fourier transform infrared spectroscopy (TGA‐FTIR), differential scanning calorimeter (DSC), and scanning electron microscopy (SEM). All the three boron compounds showed no synergistic effect with MC, and only BPO₄ at high loadings showed comparable LOI values by increasing the dripping rate. For ZnB and BSi glassy film and char formation decreases the dripping rate and sublimation of melamine and give rise to low LOI. According to TGA‐FTIR results, addition of boron compounds does not alter the gaseous product distribution of both MC and PA‐6. The addition of boron compounds affects flame retardancy through physical means. It was noted from the TGA data that boron compounds reduced the decomposition temperature of both MC and PA‐6, also affecting the flame retardancy negatively by premature degradation of MC at low temperatures. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of phosphorus flame retardants on thermo-oxidative decomposition of cotton

The effect of six organophosphorus compounds, including Pyrovatex CP (PCP), diammonium phosphate (DAP), phosphoric acid (PA), tributyl phosphate (TBP), triallyl phosphate (TAP) and triallyl phosphoric triamide (TPT) on the flame retardancy of cotton cellulose was studied. PCP, PA, and DAP are more efficient compared with the other three compounds in improving the limiting oxygen index (LOI) of cotton. The effectiveness of these compounds was investigated using scanning electron microscope (SEM) images of char formed after LOI tests, char content, activation energy of decomposition and heat of combustion data. SEM images showed that DAP, PCP and PA chars maintain the surface morphology during the burning process, which might be due to the formation of a protective layer or crosslinking effect. PA, PCP, and DAP treated fabrics have a higher activation energy of decomposition, higher char content and lower heat of combustion.     

Non-isothermal kinetics of reactions whose activation energy depends on the degree of conversion

A procedure for evaluating the non-isothermal kinetic parameters of reactions for which the activation energy depends on the degree of conversion is suggested. The procedure has been applied to the dehydration of calcium oxalate monohydrate and to the thermal degradation of poly(vinyl chloride) (PVC) and polychloroprene rubber.     

Effect of a triazine ring‐containing charring agent on fire retardancy and thermal degradation of intumescent flame retardant epoxy resins

A triazine ring‐containing charring agent (PEPATA) was synthesized via the reaction between 2,6,7‐trioxa‐l‐phosphabicyclo‐[2.2.2]octane‐4‐methanol (PEPA) and cyanuric chloride. It was applied into intumescent flame retardant epoxy resins (IFR‐EP) as a charring agent. The effect of PEPATA on fire retardancy and thermal degradation behavior of IFR‐EP system was investigated by limited oxygen index (LOI), UL‐94 test, microscale combustion calorimetry (MCC), thermogravimetric analysis (TGA) and thermogravimetric analysis/infrared spectrometry (TG‐IR). The glass transition temperatures (T_g) of IFR‐EP systems were studied by dynamic mechanical analysis (DMA). The LOI values increased from 21.5 for neat epoxy resins (EPs) to 34.0 for IFR‐EP, demonstrating improved flame retardancy. The TGA curves showed that the amount of residue of IFR‐EP system was largely increased compared to that of neat EP at 700 °C. The new IFR‐EP system could apparently reduce the amount of decomposing products at higher temperatures and promotes the formation of carbonaceous charred layers that slowed down the degradation. Copyright © 2010 John Wiley & Sons, Ltd.     

Thermal degradation study of intumescent flame retardants by TG and FTIR: Melamine phosphate and its mixture with pentaerythritol

Thermal degradation of intumescent flame retardants, such as melamine phosphate (MP) and the mixture of MP and pentaerythritol (PER) was studied by TG, FTIR gas analyser (G-FTIR), and FTIR spectrometry. The results indicate that the degradation behavior of MP or PER itself is different from the one of them in the mixture. The volatile degradation products of MP contain mainly NH₃, and H₂O, as well as small amounts of melamine (MEL), whereas no MEL is found in the degradation of the mixture of MP and PER. Moreover, degradation products of PER are composed of a lot of volatile combustibles such as formaldehydes, alcohols, and C–H compounds except for H₂O. The mixture of MP and PER, however, produces much less volatile combustibles during its degradation leading to the production of more charring materials.     

TGA/FTIR studies of segmented aliphatic polyurethanes and their nanocomposites prepared with commercial montmorillonites

Nanocomposites prepared with segmented polyurethane (SPU) and commercially available nanoclays (Cloisite™ Na⁺, Cloisite™ 15A, Cloisite™ 30B) were studied using thermogravimetric analysis coupled with Fourier Transform Infrared Spectroscopy (TGA/FTIR). The results showed that the thermal degradation of unfilled SPU and the 4, 6 and 10 wt% hand mixed nanocomposites occurred in two stages being the first due to degradation of hard segments and the second due to the degradation of soft segments. It was also found that the thermal stability of these nanocomposites was not improved by increasing nanoclay concentration except for SPU/Cloisite™ 15A nanocomposites were a 40 °C increase was observed. In a similar manner, FTIR spectra of the evolved gases obtained after the thermal degradation of these nanocomposites were qualitatively similar to the unfilled polymer except in those containing Cloisite™ 30B where isocyanate absorptions were detected. In contrast, SPU/Cloisite™ 30B nanocomposites prepared by in-situ polymerization, exhibited higher thermal stability than the corresponding hand mixed nanocomposites. In addition, these nanocomposites exhibited the presence of carbon dioxide in the evolved gases during its second degradation stage which was not observed in the hand mixed nanocomposites. In this case, it can be said that the presence of clays in the nanocomposites has a significant effect on the thermal degradation pathways.     

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.     

Preparation,flame retardancy,and thermal degradation of epoxy thermosets modified with phosphorous/nitrogen‐containing glycidyl derivative

Phosphorus/nitrogen‐containing advanced epoxy resins were obtained by chain‐extension of the diglycidyl ether of bisphenol‐A epoxy (DGEBA) resin with phosphorus‐modified triglycidyl isocyanurate (TGICP). The structure of TGICP was characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). Differential scanning calorimetry revealed that the EP/TGICP composites possessed higher glass transition temperatures than that of phosphorus free EP. The thermal stability and flame retardant properties of the epoxy resin/TGICP systems were investigated by thermogravimetric analysis (TGA), limiting oxygen index (LOI), and vertical burning test (UL‐94) test. When the TGICP content was 10 wt%, the LOI value of epoxy resin system was as high as 35.0% and it can obtain the V‐0 grade in UL‐94 protocol. From microscale combustion calorimetry (MCC) measurement, it was found that the addition of TGICP reduced the value of peak heat release rate and total heat release. The thermal degradation process of EP and EP/TGICP composite was monitored by real time FTIR. Moreover, scanning electron microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS) were used to explore the morphology and chemical components of the char residues. Copyright © 2010 John Wiley & Sons, Ltd.     

Influence of iron content on thermal stability of magnetic polyurethane foams

Magnetorheological (MR) materials are a group of smart materials which have the controllable magnetic properties with an external magnetic field. Magnetic foams, a specific type of MR solids, were synthesized from flexible polyurethane (PU) foams and carbonyl iron particles. Effects of the carbonyl iron particles on the thermal stability of the magnetic foams have been studied. Thermogravimetric analysis (TGA) was applied to characterize the thermal degradation process of the magnetic foams and then the apparent activation energy of degradation was calculated by using Ozawa's method [Ozawa T. A new method of analyzing thermogravimetric data. Bulletin of the Chemical Society of Japan 1965; 38: 1881-1886.]. The carbonyl iron particles were found to improve the thermal stability of magnetic foams in nitrogen by showing higher 10 wt% loss temperature, slower weight loss rate and higher apparent activation energy than pure PU foams. But the magnetic foams were observed to have slightly worse thermal stability in air than pure PU foams at the earlier degradation stage. At the later degradation stage, the magnetic foams exhibited the higher activation energy than pure PU foams in air.     

Synergistic effects of aluminum hypophosphite on intumescent flame retardant polypropylene system

The effects of aluminum hypophosphite(AHP) as a synergistic agent on the flame retardancy and thermal degradation behavior of intumescent flame retardant polypropylene composites(PP/IFR) containing ammonium polyphosphate(APP) and triazine charring-foaming agent(CFA) were investigated by limiting oxygen index(LOI), UL-94 measurement, thermogravimetric analysis(TGA), cone calorimeter test(CONE), scanning electron microscopy(SEM) and X-ray photoelectron spectroscopy(XPS). It was found that the combination of IFR with AHP exhibited an evident synergistic effect and enhanced the flame retardant efficiency for PP matrix. The specimens with the thickness of 0.8 mm can pass UL-94 V-0 rating and the LOI value reaches 33.5% based on the total loading of flame retardant of 24 wt%, and the optimum mass fraction of AHP/IFR is 1:6. The TGA data revealed that AHP could change the degradation behavior of IFR and PP/IFR system, enhance the thermal stability of the IFR and PP/IFR systems at high temperatures and promote the char residue formation. The CONE results revealed that IFR/AHP blends can efficiently reduce the combustion parameters of PP, such as heat release rate(HRR), total heat release(THR), smoke production rate(SPR) and so on. The morphological structures of char residue demonstrated that AHP is of benefit to the formation of a more compact and homogeneous char layer on the materials surface during burning. The analysis of XPS indicates that AHP may promote the formation of sufficient char on the materials surface and improve the flame retardant properties.     

Synthesis and properties of phosphorus-containing polyesters derived from 2-(6-oxido-6H-dibenz〈c,e〉〈1,2〉oxaphosphorin-6-yl)-1,4- hydroxyethoxy phenylene

A series of phosphorous-containing aliphatic polyesters were synthesized by high-temperature solution condensation of 2-(6-oxido-6H-dibenz〈c,e〉〈1,2〉oxaphosphorin-6-yl)-1,4-hydroxyethoxy phenylene (III) with various aromatic acid chlorides in o-dichlorobenzene. All polyesters are amorphous and readily soluble in many organic solvents such as DMAc, NMP, DMSO, and o-dichlorobenzene at room temperature or upon heating. These polyesters are thermally quite stable. The glass transition temperatures of these aliphatic polyesters ranged from 126.6 to 162.2°C. The degradation temperatures (T_d onset) in nitrogen ranged from 424 to 448°C, and the char yields at 700°C are 20–32%. The activation energies of degradation ranged from 160.9 to 226.0 kJ/mol. The LOIs of these polyesters ranged from 36 to 43. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3051–3061, 1998     

Synthesis and property of phosphorus‐containing bismaleimide by a novel method

A series of novel addition products (phosphorus content: 0.5, 1, 2, and 3 wt %) were synthesized from the reaction of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐oxide (DOPO) and 4,4′‐bismaleimidodiphenylmethane (BMI). NMR and IR were used to confirm the structures of the synthetic bismaleimides. Dynamic mechanical analysis scans showed the glass‐transition temperatures of these cured BMIs decreased with phosphorus content. Thermal gravimetric analysis heating scans indicated that they had high thermal stability. Limiting oxygen index measurements implied that the flame retardancy was improved by the incorporation of DOPO. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2260–2268, 2000     

Thermal degradation and flame retardancy of polynorbornene by a zeolite

The relation between the thermal decomposition and flammability of polynorbornene (PNB) synthesized by addition polymerization was analyzed. In a small-sized vertical combustion test, the PNB did not combust or drip, and the first ignition was extinguished in the combustion test with a cone calorimeter. The decomposition products of PNB were of some low molecular weight compounds with random scissions on the norbornene structure, and alkene (with 12 carbons in the PNB used in this study) was selectively generated by retro-Diels-Alder reaction. When the zeolite was added, the decomposition was accelerated and low molecular weight products increased, especially H₂O. These results suggested that the flammability of the thermal decomposition gas was caused by the zeolite, which changed the composition of decomposition products. The lower flammability limits calculated in Le Chatelier's equation were increased from 0.9 to 1.3 by the zeolite. The flame retardancy of PNB was observed because the amount of H₂O as an inert gas and the lower flammability limit was increased.     

Effects of synthetic and natural zeolites on morphology and thermal degradation of poly(lactic acid) composites

Poly(lactic acid) (PLA) composites containing 5 wt% synthetic (type 4A) and natural (chabazite) zeolites were prepared using extrusion/injection molding. Morphological, structural, and thermal properties of composites were investigated by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC). DSC results revealed that the glass transition and melting temperatures were not significantly changed; however, the incorporation of both type 4A and chabazite zeolites enhanced the nucleation of PLA crystallites as well as increased the percent crystallinity. Thermal degradation properties of PLA and PLA/zeolite composites were studied by non-isothermal thermogravimetric analysis (TGA) in nitrogen atmosphere. TGA results showed that at temperatures above 300 °C, PLA/type 4A synthetic zeolite composites were thermally decomposed more easily than the PLA and PLA/chabazite natural zeolite composites. The apparent activation energies of thermal degradation of PLA and PLA/zeolites composites estimated using both the Flynn-Wall-Ozawa and Kissinger methods followed the same order: PLA/type 4A < PLA/chabazite < PLA.