abstract: Flame retardants (FRs) are applied to variety of consumer products such as textiles and polymers for fire prevention and fire safety. Substantial research is ongoing to replace traditional FRs with alternative materials that are less toxic, present higher flame retardancy and result in lower overall exposure as there are potential health concerns in case of exposure to popular FRs. Carbonaceous nanomaterials (CNMs) such as carbon nanotubes (CNTs) and graphene oxide (GO) have been studied and applied to polymer composites and electronics extensively due to their remarkable properties. Hence CNMs are considered as potential alternative materials that present high flame retardancy. In this research, different kinds of CNMs coatings on polyester fabric are produced and evaluated for their use as flame retardants. To monitor the mass loading of CNMs coated on the fabric, a two-step analytical method for quantifying CNMs embedded in polymer composites was developed. This method consisted of polymer dissolution process using organic solvents followed by subsequent programmed thermal analysis (PTA). This quantification technique was applicable to CNTs with and without high metal impurities in a broad range of polymers. Various types of CNMs were coated on polyester fabric and the efficacy of coatings as flame retardant was evaluated. The oxygen content of CNMs emerged as a critical parameter impacting flame retardancy with higher oxygen content resulting in less FR efficacy. The most performant nanomaterials, multi-walled carbon nanotubes (MWCNTs) and amine functionalized multi-walled carbon nantoubes (NH2-MWCNT) showed similar FR properties to current flame retardants with low mass loading (0.18 g/m2) and hence are promising alternatives that warrant further investigation. Chemical/physical modification of MWCNTs was conducted to produce well-dispersed MWCNT solutions without involving oxygen for uniform FR coating. The MWCNTs coating was studied to evaluate the durability of the coating and the impact on the efficacy during use phase by conducting mechanical abrasion and washing test. Approximately 50% and 40% of MWCNTs were released from 1 set of mechanical abrasion and washing test respectively. The losses during simulated usage impacted the flame retardancy negatively. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2018

Tris(1-chloro-2-propyl) phosphate (TCPP) and tris(1,3-dichloro-2-propyl) phosphate (TDCPP) are added to polyurethane foams in a variety of industrial and consumer products to prevent flame ignition. The gradual release of these flame retardants (FRs) from such products leads to contamination of various abiotic and biotic media, including wild birds. Recent studies demonstrated endocrine-disrupting effects of TCPP and TDCPP, including alteration of circulating thyroid hormone (TH) levels. The TH-pathway is essential for normal growth and development in birds. There are limited data on the toxicological effects of TCPP and TDCPP in avian species and, prior to this work, no study has examined their effects in avian embryos. This M.Sc. thesis investigates the developmental, molecular and biochemical effects of TCPP and TDCPP in chicken (Gallus gallus domesticus) embryos via egg injection studies. TCPP delayed pipping at doses ≥9.24 μg/g, both TCPP and TDCPP reduced embryo growth at the highest dose (51.6 μg TCPP/g and 45 μg TDCPP/g), and TDCPP decreased free plasma thyroxine and gallbladder size at 7.64 μg/g and 45 μg/g, respectively. Real-time reverse transcription polymerase chain reaction was used to measure changes in mRNA levels of hepatic genes that were responsive to these FRs in a previous in vitro study. TCPP dysregulated the expression of TH-responsive genes and xenobiotic metabolizing enzymes (cytochrome P450s; CYPs), whereas TDCPP only affected CYPs. Less than 1% of the administered TCPP or TDCPP was detected in egg contents following 19 days of incubation, indicating extensive metabolism of the parent compounds. DNA microarrays were used to perform a global transcriptional analysis on liver samples from embryos that exhibited adverse effects following TDCPP injection. 47 differentially expressed genes were identified at the 45 μg/g dose. Functional analysis revealed that immune function and lipid and steroid metabolism were major targets of TDCPP toxicity and indicated a state of cholestatic liver/biliary fibrosis. Since the TH-pathway is a key regulator of metabolic homeostasis, its disruption early in development is a potential cause of the observed adverse effects. This thesis demonstrates, for the first time, developmental and endocrine-disrupting effects of TCPP and TDCPP in an avian species and attempts to link phenotypic changes to molecular-level disruptions in hopes to improve the understanding of their modes of action.

Depuis Juillet 2008, l'union européenne bannit une grande partie des retardateurs de flamme halogénés actuellement sur le marché pour des problèmes environnementaux. Les produits phosphorés s'avèrent une alternative prometteuse. Dans le cadre de ma thèse, nous décrivons la synthèse de monomères allyliques phosphonés cycliques, leur télomérisation, polymérisation et copolymérisation en solution par voie radicalaire mais aussi les premiers « essais feu» effectués. Les monomères allyliques phosphonés cycliques sont synthétisés par transestérification entre un glycol possédant une double liaison et un hydrogénophosphonate. La présence de diastéréoisomères nous a permis de faire une étude poussée en RMN pour comprendre la structure de ces composés. L'homopolymérisation radicalaire du dioxaphosphorinane hydrogéné faite en présence d'AIBN comme amorceur nous a permis d'obtenir des polymères avec 2 distributions chromatographiques composées d'oligomères et de polymères de haute masse moléculaire respectivement. Cette deuxième espèce présente une structure hyperbranchée avec des solubilités faibles qui nuisent aux futures applications. Des solutions alternatives ont été proposées comme la télomérisation de ce même monomère avec l'hydrogénophosphonate de diméthyle comme agent de transfert donnant une seule population d'oligomères. Le remplacement de l'hydrogène lié au phosphore par un groupement alkyle ou aryle simplifient le mécanisme de polymérisation pour former des chaînes macromoléculaires où les groupements phosphonés sont situés dans les chaînes latérales. La copolymérisation Accepteur/Donneur entre l'anhydride maléique et les allyl éthers phosphonés a été envisagée pour produire des copolymères alternés avec la possibilité d'introduire des groupements différents comme les acides carboxyliques, potentiellement intéressants pour la résistance au feu. Une dernière solution, utilisant la synergie des atomes d'azote et de phosphore, a été mise en oeuvre par la synthèse d'oligomères allyl amine phosphonés par polymérisation radicalaire en solution aqueuse. Un bilan de tous les polymères phosphonés a été réalisé dans le but de tester leurs performances en tant que retardateurs de flamme. Les caractérisations en analyse thermogravimétrique et en microcalorimètre ont montré une bonne thermostabilité des télomères comme des copolymères et une chaleur dégagée équivalente au produit de référence. Les essais feu sur textile au cône calorimètre montrent que des résultats encourageants sur les polymères synthétisés. / Since July 2008, a wide rnage of halogenated flame retardants was withdrawed from the market for environmental problems by the European Union. The phosphorous products turn out to be promising candidates. Within the framework of my thesis, the synthesis of allyl cyclic phosphonated monomers is described as well as their telomerization, polymerization and copolymerization in solution using a radical process). Their flame retardant behavior was also evaluated. Allyl cyclic phosphonated monomers are synthesized by transesterification between a glycol with a double bond and hydrogenophosphonate. An NMR study of the obtained diastereoisomers allowed us to fully understand the structure of these compounds. Radical homopolymerization of hydrogenated dioxaphosphorinane, in the presence of AIBN as initiator, allowed us to obtain polymers with two molar mass distributions: one for oligomers and one for polymers of higher molar mass. This second species is due to a hyperbranched structure showing poor solubility in common solvents, which damage the future applications. The telomerization of the same monomer was carried out using dimethyl hydrogenophosphonate as chain transfer agent leading only one population of oligomers. Furtehrmore, the replacement of the hydrogen linked to phosphorus by an alkyl or aryl group simplify the mechanism of polymerization since only linear oligomers are obtained. Acceptor-donor copolymerization of maleic anhydride and phosphonated allyl ethers, allowed producing alternated copolymers with the opportunity to introduce different reactive groups such as carboxylic acids. Then, oligomers were produced by radical polymerization of phosphonated allyl amine in order to potentially use the nitrogen-phosphorus synergy. An overview of all the phosphonated polymers previously synthesized, was done with the aim of testing their flame retardant performances. Thermogravimetric analysis showed a good thermal behavior of the telomers and the copolymers, similar heat release rate was observed by microcalorimeter compare to commercial product. High efficiency of these phosphorus-containing flame retardants polymers was finally evidenced by using the cone calorimeter on textile.

In the pursuit of lower cost intumescent flame retardant (IFR) systems, the compound expandable graphite (EG) was identified. This compound delivers high flame retardant performance but provides non-uniform thermal shielding when exposed to open flame from below due to negative gravitational effects. It was theorised that this may be remedied either through ion exchange of the interstratified ions with low glass transition ions or through use in binary systems with other compounds. Two classes of commercial EG were identified, namely a low and a high expansion onset temperature EG compound. Extensive characterisation of each EG compound was undertaken to assess its composition, expansion mechanisms and onset temperatures in order to identify compatible compounds for binary use. The susceptibility of each compound to ion exchange was also assessed. An industrial IFR ethylenediamine phosphate (EDAP) and a novel flame retardant were synthesised for assessment in binary use with EG. Coupled with the above study, this project developed two novel fire testing techniques as low cost alternatives to well-established fire testing methods such as cone calorimetry. The first technique involved an open flame fire testing method which allowed vertical or horizontal testing. Digital and infrared (IR) video recording during operation facilitated comparison of multiple performance indicators further strengthening this method. The second technique allowed assessment of the mass loss resistance of each compound during laser pyrolysis. Characterisation of the EG compounds allowed development of structural models to describe each compound and explain the mechanisms of their expansion and gaseous release. Exhaustive ion exchange testing did not deliver favourable results, necessitating the pursuit of compounds for binary use with EG. A novel IFR was synthesised by neutralising 3,5-diaminobenzoic acid hydrochloride salt with ammonium dihydrogen phosphate. This compound, which melts at 257 °C, decomposes concurrently to release carbon dioxide gas which promotes intumescent charring. The flame retardant performance of this compound and EDAP as primary flame retardants and in combination with expandable graphite was evaluated. As a proof of concept, the novel compound was tested as a primary flame retardant using cone calorimetry after which its utility in binary systems with low temperature expandable graphite was tested. Substantial decreases in peak heat release rate (pHRR) and flame out time were achieved for all binary systems. This success led to testing of a number of combinations of low and high expansion onset EG and the other IFRs to identify the highest performing combination, which proved to be the 10-10 EDAP-EG system. Combinations of EG and the novel compound also showed excellent results. The novel fire testing techniques proved effective in identifying high performance combinations and showed comparable trends to those measured in cone calorimetry, at a greatly reduced cost and material requirement. IR analysis of open flame fire testing indicated increases in the temperatures required for ignition and burn through of the substrate. Observations, corroborated by optical video, showed that cohesive and uniform thermal shielding was achieved in all binary systems tested. This study illustrates that systems of 10% EG combined with either 10% DABAP or 10% EDAP are both the most economical binary systems tested but are extremely high performance systems as well. Both of these systems delivered excellent results while being more economic than the widely used industrial system with a 25-30% EDAP loading. It is recommended that these compounds be considered for industrial use. Furthermore, the effective fire testing techniques developed in this study may be utilised in future fire testing to identify high performance compounds at a lower cost prior to further assessment through methods such as cone calorimetry. / Thesis (PhD)--University of Pretoria, 2017. / Chemical Engineering / PhD / Unrestricted

Flame retardant chemicals were used to make flammable fibres or fabrics flame retardant. Flame retardants protect the flammable material from fire by delaying or preventing the ignition process. The problem with flame retardants is unreliable durability when applied physically or bonded chemically on the surface of the fibre or fabric. This thesis project investigated the implementation of inherently flame retardant fibres as a shield form flame for flammable fibres. The most widely used flammable textiles fibres (cotton and polyester) were mixed with inherently flame retardant fibres (modacrylic and Lenzing FR) pairwise at fibre level for non-woven fabric and both fibre & yarn level for knitted fabric. The vertical flame test, where the fabric hung vertically and burned from the bottom, was used to characterise their burning behaviour. With the vertical flame test, it was found that flame shielding ability of inherently flame retardant fibres towards flammable fibres improves with an increasing proportion of inherently flame retardant fibres in the fabric. Also, fabric structure influences the shielding properties of the flame retardant fibres. A comparison between fibre and yarn level mixing for knitted fabric yarn level mixing was found to have better flame shielding properties. Thesis work points out the issue with flame retardant chemical and presents an alternative approach for conventional flame retardant.

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Bulk atmospheric deposition samples were taken every two months for a year in 2009-2010 at two sites in northern Sweden and analyzed for a suite of legacy and emerging persistent organic chemicals including legacy organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs)  and novel flame retardants (NFRs).  To further investigate the urban occurrence and contribution to remote contamination of flame retardants, indoor air, ventilation system air, and dust were sampled in several microenvironments in Stockholm during the winter of 2012 for analysis of PBDEs, isomer-specific hexabromocyclododecane (HBCDD), and NFRs.  Outdoor air and soil samples were also sampled around the same time period for analysis of the same compounds.  Five emerging pollutants were detected in atmospheric deposition: the current-use pesticides trifluralin and chlorothalonil; and the NFRs 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), 1,2-bis(tribromophenoxy)ethane (BTBPE), and Dechlorane Plus (DP).  A decrease in the fraction of the anti isomer of DP was observed at the more remote site, indicating isomer-selective degradation or isomerization during long range atmospheric transport.  The more remote site also received more total deposition of organic pollutants despite its receiving less precipitation.  Although PBDEs and emerging organic pollutants were detected, the bulk of the deposition consisted of PCBs and hexachlorocyclohexanes (HCHs) at both sites.   Several NFRs were identified in indoor and ventilation air samples including TBECH, pentabromotoluene (PBT), hexabromobenzene (HBB), 1,2-bis(pentabromodiphenyl)ethane (DBDPE), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTBB), and bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (TBPH).  There was no significant difference between concentrations of contaminants in ventilation system air and indoor air indicating that the flame retardants included in this study reach the outdoor environment via ventilation systems.  Dust and outdoor air samples have only been analyzed for HBCDDs so far.  HBCDD concentrations in apartments, offices, and schools were lower than reported concentrations for other countries in similar microenvironments.   However, an enrichment of α-HBCDD compared to γ-HBCDD was observed in dust taken from near treated products in stores when compared to dust taken directly from those products.  Very low concentrations of HBCDDs were detected in outdoor air.

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