Commercial fire-retarded PET formulations - relationship between thermal degradation behaviour and fire-retardant action

Many types of fire-retardants are used in poly(ethylene terephthalate), PET, formulations, and two commercial fire retardants, Ukanol(TM) and Phosgard(TM), have been shown to improve significantly PET flame-retardancy when used as comonomers. Phosgard incorporates a phosphorus atom within the main chain whereas Ukanol incorporates a phosphorus atom as a pendent substituent. Despite their acknowledged effectiveness, the mode of action of these fire retardants remains unclear, and in this paper we present a comparison of the overall thermal degradation behaviour of PET and Ukanol and Phosgard fire retarded formulations. DSC and particularly TGA data show that both Ukanol and Phosgard have some stabilising influence on PET degradation, especially under oxidative conditions. TGA and pyrolysis experiments both clearly indicate that neither additive acts as a char promoter. Only the Phosgard formulation shows any release of volatile phosphorus species which could act in the gas phase. On the other hand, the most striking feature of the pyrolysis experiments is the macroscopic structure of the chars produced by the fire-retarded formulations, which hints at their fire-retardancy action - an open-cell charred foam was obtained upon charring at 400°C or 600°C. This foaming layer between the degrading melt and the flame would lower the amount of fuel available for combustion, and would also limit the feedback of heat to the condensed phase

Oxidative and non-oxidative degradation of a TDI-based polyurethane foam : volatile product and condensed phase characterisation by FTIR and solid state 13C NMR spectroscopy

The oxidative and non-oxidative degradation behaviour of a flexible polyurethane foam, synthesised from toluene diisocyanate and a polyether polyol, is reported. Both toluene diisocyanate and diaminotoluene were identified as major products under non-oxidative conditions, which indicates that the urethane linkages are degrading by two competing degradation mechanisms. Degradation of the urethane linkage by a depolymerisation reaction to yield toluene diisocyanate and polyol is proposed to occur initially. In addition, the atmospheric pressure conditions favour the degradation of the urethane linkages via a six-membered ring transition state reaction to form diaminotoluene, carbon dioxide and alkene terminated polyol chains. Solid-state 13C NMR spectroscopy and elemental analysis of the residues indicates that at temperatures above 300°C ring fusion of the aromatic components within the foam occurs, and this leads to a nitrogen-containing carbonaceous char which has a complex aromatic structure. It is proposed that under the confined conditions of the degradation the aromatic nitrogen-containing species, such as toluene diisocyanate and diaminotoluene, undergo secondary reactions and ring fusion to yield a complex char structureUnder oxidative conditions, degradation, including ring fusion, occurs at a lower temperature than under non-oxidative conditions. Neither toluene diisocyanate nor diaminotoluene were observed as major degradation products. The polyol is observed to undergo thermo-oxidative degradation at much lower temperatures than purely thermal degradation. As a consequence, the depolymerisation reaction via the six-membered ring transition state is limited in extent and diaminotoluene is not evolved. The absence of toluene diisocyanate is proposed to be a result of this species undergoing oxidative degradation reactions which lead to it being incorporated into the char

Developing and applying an integrated modular design methodology within a SME

Modularity within a product can bring advantages to the design process by facilitating enhanced design reuse, reduced lead times, decreased cost and higher levels of quality. While the benefits of modularity are becoming increasingly better known, at present it is usually left to the designers themselves to introduce modularity into products. Studies into modularity have shown that byimplementing 'formal' methods, further benefits can be made in terms of time, cost, quality and performance. Current approaches that have been proposed for the formal development of modular design methodologies fail to accurately represent knowledge that is inherently produced during design projects and fail to consider design from the different viewpoints of the development process. This work, built on previous work on modularity and design for reuse, aims to develop an integrated design methodology that will optimise the modules created through the design process and allow for modularity to be 'built-in' to product development from the initial stages. The methodology andassociated tools have been developed to provide an easy-to-use approach to modularity that has support for design rationales and company knowledge that aid in effective design decision making. The methodology, named GeMoCURE, provides an integrated total solution to modular design based on reuse of proven physical and knowledge modules. Its incremental nature allows for the optimalstructure to be maintained as the design progresses. A special focus has been on the application of this approach for Small to Medium Enterprises (SMEs), which are typically challenged by a lack of design human resources and expertise

An investigation of the nature and reactivity of the carbonaceous species deposited on mordenite by reaction with methanol

An investigation of the nature of the carbonaceous species deposited upon mordenite by reaction with methanol has been undertaken. The nature of the species has been shown to be a strong function of both temperature and time on stream. Upon reaction at 300 degrees C a range of alkyl and aromatic species, consistent with the development of an active hydrocarbon pool, are evident and time on stream studies have shown that these are developed within 5 min. Upon reaction at 500 degrees C, a narrower range of hydrogen deficient aromatic species is evident. Thermal volatilisation analysis (TVA), not previously applied to the study of coked zeolites, is shown to be complementary to the more commonly applied C analysis, C-13 MAS NMR and TGA techniques

Thermal degradation of Cross-Linked Polyisoprene and Polychloroprene

Polyisoprene and polychloroprene have been cross-linked either in solution or in solid state using free radical initiators. In the comparable experimental conditions higher cross-linking density was observed in the solid state process. Independent of the cross-linking method, polychloroprene tended to give a higher gel content and cross-link density than does polyisoprene. Infrared characterization of the cross-linked materials showed cis-trans isomerization occurred in the polyisoprene initiated by benzoyl peroxide, whereas no isomerization was found in the samples initiated by dicumyl peroxide. Polyisoprene does not cross-link by heating in a thermal analyzer, whereas polychloroprene easily undergoes cross-linking in such conditions. Infrared spectroscopy showed that in the case of polyisoprene, rearrangements occur upon heating which lead to the formation of terminal double bonds, while polychloroprene loses hydrogen chlorine which leads to a conjugated structure. There is apparently some enhancement of the thermal and thermal oxidative stability of polyisoprene because of the cross-linking. Cross-linked polychloroprene is less thermally stable than the virgin polymer. Cross-linking promotes polymers charring in the main step of weight loss in air, which leads to enhanced transitory char

A simple chemical approach to regenerating strength of thermally damaged glass fibre for reuse in composites

A key technical barrier to the reuse of thermally recycled glass fibres in composite applications is their low mechanical strength. This research study looks into the effect of alkaline treatments in regenerating the strength of glass fibres which were heated in a furnace to simulate thermal recycling conditions. Up to 100% strength increase of the fibres can be achieved through a simple treatment in alkaline solution. It was found that the nature of alkali, concentration, and treatment duration had a significant effect on the extent of strength recovery of the fibres. These treatments could potentially be implemented to thermally recycled glass fibres on an industrial scale, to allow their reprocessing into second-life composite materials. As well as optimising the reaction conditions to regenerate fibre strength, an examination of the surface morphology was carried out using various techniques. In addition, the kinetics of dissolution of glass fibres in alkaline solutions was investigated in order to further understand the strength regeneration mechanism

The thermal degradation behaviour of a series of siloxane copolymers - a study by thermal volatilisation analysis

The thermal degradation behaviour of novel high number average molecular mass polysilalkylenesiloxanes is reported. These have been synthesised using anionic ring-opening polymerisation of 1,1,3,3,14,14,16,16-octamethyl-2,15-dioxa-1,3,14,16-tetrasilacyclohexacosane and octamethylcyclotetrasiloxane (D4) mixtures. The thermal degradation behaviour of these materials was evaluated by a combination of thermogravimetric analysis (TGA) and thermal volatilisation analysis (TVA) and compared with a commercial sample of PDMS. The results demonstrated that the thermal degradation of the polysilalkylenesiloxanes is more complex than the PDMS, with the polysilalkylenesiloxanes exhibiting a lower degradation peak maximum temperature. The major volatile degradation products evolved from the PDMS were identified as D3 to D6 cyclic siloxane oligomers, in addition to higher molecular mass cyclic siloxane oligomers. The polysilalkylenesiloxanes, on the other hand, evolved short chain aliphatic hydrocarbons, cyclic and linear siloxane oligomers and silanes. The TVA results indicate that the polysilalkylenesiloxanes degrade mostly by random chain scission of the polymer backbone, whereas the commercial PDMS degrades by the accepted depolymerisation reaction which involves “back-biting” reactions

Evaluation of thermal properties and crystallinity in PHB-based systems - a DoE approach

Complex formulations based on poly(hydroxybutyrate) (PHB) and poly(hydroxybutyrate-co-valerate) (PHBV) were studied to statistically assess the effect of formulation (i.e., hydroxyvalerate (HV) content, plasticiser chemistry and content, filler type and content) on their thermal properties and degree of crystallinity (Xc). In binary systems, thermal properties were mainly influenced by filler type rather than its content, while for plasticised systems the changes were dependent on both increasing plasticiser content and PHB-plasticiser compatibility. Variations in HV content affected the ability of the polymer chain to fold, leading to significant changes in both thermal properties and Xc. In ternary systems, presence of multiple additives and consequent changes in intermolecular interactions lead to multifaceted behaviours that were not easily predicted by results from binary systems alone. For example, melting temperature did not show dependence on filler presence in PHBV systems despite introducing variations in pure PHB systems. In general, thermal properties and Xc are affected by all parameters studied, with changes in system free volume (i.e. changes in HV content and plasticisation) playing the most significant role. These results expand the understanding of factors controlling crystallisation in complex polymer systems and can be used to control matrix properties in new generations of packaging materials

A Study of the Ceramicisation of Allylhydridopolycarbosilane by Thermal Volatilisation Analysis and Solid-State Nuclear Magnetic Resonance

AHPCS is a pre-ceramic polymer utilised as a precursor to SiC. An initial polymerisation to a cross-linked network is followed by a complex sequence of processes ultimately leading to amorphous SiC. Using thermal volatilisation analysis (TVA) accompanied with solid-state NMR (SSNMR), FTIR, MS, DSC and TGA the complete thermal profile was identified. Between 160 – 300 °C, AHPCS cross-links through the allyl group and undergoes some carbon-silicon rearrangement, with a volatilisation of low mass oligomeric material and significant volumes of hydrogen released from dehydrocoupling of SiH moieties. By 300 °C the allyl group is completely cross-linked but the polymer starts to undergo pyrolytic degradation of the network, with the release of chain fragments and low molar mass species such as methane, ethane, methanol, propane, propene and silane species. Hydrogen once again becomes the major volatile product above 400 °C due to higher proportion of dehydrocoupling forming Si–C and Si–Si bonds. Small chain fragments are seen in the form of larger alkyl silanes. These fragments come from the chain scission of the polymer at weaker parts of the network. The process of side group scission leads to further radical recombination reactions of silicon and carbon atoms to build the SiC network. By 500 °C higher proportion of dehydrocoupling occurs with recombination of Si–Si and Si–C species. The Si–H bonds in -SiH3 groups have completely cleaved along with C-H bonds in the CH3 and CH2 groups leaving SiC, -SiH and HCSi3 present in the material. This bond cleavage leads the silicon and carbon radical species to undergo radical recombination in the network with the volatile release being dominated by H2. By 650 °C the cleavage and recombination of remaining -SiH2-, -SiH- and HCSi3 groups ultimately form amorphous SiC. The volatiles released are mostly hydrogen with very few condensable products seen. Finally, SiC is then crystallised at higher temperatures forming β-SiC at 1100 °C and then subsequently α-SiC above 1500 °C

The thermo-oxidative degradation of poly(4-methylstyrene) and its relationship to flammability

Polystyrene and poly(4-methylstyrene) have very similar chemical structures with the only differences being the para methyl group of poly(4-methylstyrene). This methyl group is susceptible to oxidation at elevated temperatures. Here we demonstrate that it is possible to introduce oxidative cross-links to poly(4-methylstyrene), via the para methyl group, by thermal oxidative treatment at 230 °C, 250 °C and 270 °C in the absence of catalyst, leading to a material with markedly modified thermal degradation chemistry. Thermal gravimetric analysis and differential scanning calorimetry were used to characterise and compare untreated and post-oxidised materials and established that as the temperature of pre-treatment was increased, the subsequent thermal stability of the material increased. FTIR, NMR and microanalysis indicated that after the thermal oxidative pre-treatment ether cross-links are present alongside new oxygen containing functional groups such as aldehydes, carboxylic acids and hydroxyl groups. Finally, data obtained from pyrolysis combustion flow calorimetry confirmed that as the number of oxidative cross-links increase, a reduction in the polymer's flammability as assessed by heat release data is observed