Polymer Degradation and Stability (v.96, #3)

Calendar (I-II).

FRPM 09’ Special Issue PDS by Maria Wladyka-Przybylak; Izabela Maciejowska (255).

Three systems of FR treatments of polyamide 6 with conventional flame retarding additives in the absence and in the presence of nanoparticles are discussed: I. ammonium sulfamate (AS) and dipentaerythritol (Di) II. melamine cyanurate (MC) III. pentabromobenzyl acrylate in the monomeric (PMA) and the polymeric (PPA) form. Depending on the concentration of the nanoparticles; synergism, antagonism, and cooperation in flame retardancy as well as in mechanical properties are observed. Cooperation between the OMMT in the concentration range of 0.5–1.0 wt% and the FR in all three systems is observed. The decrease in PHRR (ΔPHRR) is different for the three systems. In system III the brominated FR behaves similarly to OMMT with respect to ΔPHRR. The interaction between the molten polymeric matrix and the nanoparticles increases the viscosity in all three systems, which slows down the supply of the flame retarding moieties to the flame and lowers the FR rating, as measured by the UL-94 and OI tests. A new approach for assessing the viscosity of the pyrolyzing nanocomposite is presented by determining the size and mass of the drops formed during the UL-94 test. Dispersion of the nanoparticles in the polymer decreases the HRR and MRR and decreases the UL-94, OI ratings, and the mechanical properties, as evidenced by the different behavior of OMMT and Na+MMT. The time of ignition decreases markedly by the addition of the nanoparticles, due to the low thermal conductivity and heat transfer of the protective barrier on the surface of the pyrolyzing nanocomposite in the pre-ignition phase. A possibility of restoring the high FR rating in the presence of higher concentrations of nanoparticles is indicated. The significance of the results obtained for the future of the use of nanoparticles in FR is discussed.
Keywords: Flame retarding PA6; Synergism; Time of ignition; Migration; Rate of heat release; Pentabromobenzyl acrylate;

Polystyrene based nanocomposites (PNCs) with and without flame retardant additives were successfully prepared through a single-screw extrusion technique. The combination effect of nanoparticles and flame retardants was investigated with nanosilica and attapulgite clay as nanofillers, and with a NASA formulated SINK flame retardant. A comprehensive study was done by Cone Calorimetry, UL94 and TGA.The addition of nanoparticles to polystyrene generally improved the OI of polystyrene. The horizontal burning tests suggested that nanofiller types have different impacts on the flammability of nanocomposites. According to the vertical burning tests and oxygen indices, it was found that polystyrene/silica and polystyrene/attapulgite clay PNCs alone are not flame retardant. In fact, the materials burned faster. However, the combination of nanocomposites with the SINK flame retardant significantly altered the thermal stability, and flammability of the materials. A remarkable reduction in heat release rates of polystyrene was achieved for both silica and attapulgite with flame retardant nanocomposites. For instance, the introduction of 20% SINK into PS reduced the PHRR of PS from 1212 to 838 (−31%); 10% silica reduced it from 1212 to 1060 (−13%), while the combination of silica and SINK reduced it to 530 (−56%), which clearly shows interaction between nanosilica and SINK.
Keywords: Polystyrene; Flammability; Thermal stability; Combination; Cone calorimetry;

Polyamide 6 (PA 6) and polypropylene (PP) containing fire retardants, nanofillers or a combination of both additives have been investigated using the steady state tube furnace (ISO TS 19700). The samples were tested under three different fire conditions, to determine the effect of additives on the soot production or toxic product yields. The particle size distribution of the soot was investigated with a cascade impactor, and the separated soot fractions examined by SEM. The predicted deposition based on aerodynamic size of particulates in the human respiratory tract shows clear differences between the pure polymer and its additive counterparts. In all ventilation conditions the virgin polymer produces the least amount of soot, both the additives used (fire retardant and nanoclay) increase the amount of soot, mainly within 0.5–1.0 μm range, for each fire condition. A large contribution to the total soot mass originated particles smaller than 0.5 μm.
Keywords: Fire; Toxicity; Nanocomposites; Retardant; Soot; Cascade impactor;

Thermal degradation behaviors of a novel nanocomposite based on polypropylene and Co–Al layered double hydroxide by De-Yi Wang; Amit Das; Andreas Leuteritz; Regine Boldt; Liane Häußler; Udo Wagenknecht; Gert Heinrich (285-290).
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.
Keywords: Polypropylene (PP); CoAl-LDH; Thermal degradation behaviors; Fire retardancy;

Flammability, structure and mechanical properties of PP/OMMT nanocomposites by Konrad Szustakiewicz; Adam Kiersnowski; Małgorzata Gazińska; Krzysztof Bujnowicz; Jacek Pigłowski (291-294).
Polypropylene/organoclay (PP/OMMT) nanocomposites were prepared in a twin-screw corotating extruder using two methods. The first method was the dilution of commercial (PP/50% Nanofil SE3000) masterbatch in PP (or PP with commercial flame retardant). The second method consists of two stages was the extrusion of maleic anhydride grafted polypropylene (PP-g-MAH) with commercially available organobentonite masterbatch in first stage and dilution of the masterbatch in PP (or PP with commercial flame retardant) in second stage. XRD results showed no intercalation in composites obtained from commercial masterbatch without compatibilizer and semi – delamination for compatibilized systems. Tensile tests revealed that nanocomposites with 5% of organoclay have a slightly higher tensile modulus and tensile strength than pristine PP, however addition of the commercial flame retardant (FR) reduces mechanical parameters to roughly the level of those for neat PP. PP/OMMT composites have approx. 25% higher oxygen index than pristine PP, and this changes slightly after the addition of FR. The cone calorimeter tests showed a decrease of a heat release rate (HRR) and a mass loss rate (MLR) after the addition of FR.
Keywords: Polypropylene; Organoclay; OMMT; Nanocomposites; Flammability; XRD;

Polypropylene (PP) and Polyamide 6 (PA6) samples, with and without fire retardants (FR) (ammonium polyphosphate in PP, and a mixture of organic aluminium phosphinate and melamine polyphosphate (OP 1311) in PA 6) and nanofillers (NC) were burned under different fire conditions in order to compare their toxic product yields. Fire effluents (CO, smoke and hydrocarbons) were generated using a steady state tube furnace (BS 7900, ISO TS 19700) for the separate materials and fire retarded and nanocomposite modifications of these materials under flaming conditions. Under well-ventilated conditions yields of carbon monoxide (CO) for all PP samples are similar, whereas for PA6 samples much higher yields of CO for PA6 + FR and PA6 + NC are observed. The highest yields of CO occur for both pure polymers in under-ventilated fire conditions when fire retardant and nanoclay are combined together. For PP the smoke is fairly independent of fire condition, but the PP + FR + NC shows less agglomeration. For PA6 the sample containing OP 1311 shows consistently higher smoke yields. For hydrocarbon yields similar effects are observed for both PP and PA6 polymers; the highest yields are for PA6 + NC, except under-ventilated fires where PA6 + FR produce the most; for PA6 + FR + NC samples the lowest yields are observed, compared to either NC or FR formulations.
Keywords: Fire; Smoke; Hydrocarbon; Soot; Fire retardant; Nanocomposites;

EVA-layered double hydroxide (nano)composites: Mechanism of fire retardancy by Xiaolan Wang; Rajendra Rathore; Ponusa Songtipya; Maria del Mar Jimenez-Gasco; Evangelos Manias; Charles A. Wilkie (301-313).
Composites of ethylene–vinyl acetate copolymer with two different layered double hydroxides have been obtained by melt blending and these have been characterized by X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, thermogravimetric analysis connected to mass spectroscopy and cone calorimetry. There is some small difference in dispersion between the zinc-containing and the magnesium-containing layered double hydroxides in EVA, but both these are microcomposites with good dispersion at the micrometer level and relatively poor dispersion at the nanometer level. There is a good reduction in the peak heat release rate at 10% LDH loading. In addition to chain stripping, which involves the simultaneous loss of both acetate and a hydrogen atom, forming acetic acid, and the formation of poly(ethylene-co-acetylene), side chain fragmentation of the acetate group also occurs and may be the dominant pathway of thermal degradation in the first step. The presence of the LDH causes acetone, rather than acetic acid, to be evolved in the initial step of the degradation.
Keywords: EVA; TGA/FTIR/MS; Fire retardancy; Cone calorimetry;

Determination of the flammability properties of polymeric materials: A novel method by R. Carvel; T. Steinhaus; G. Rein; J.L. Torero (314-319).
Standard flammability tests, like the Cone Calorimeter, were developed several decades ago and provided sufficient flammability data for the purposes of the time. However, recent pyrolysis models have revealed the limitations of the standard test in providing adequate data for current flammability analysis and modelling. This paper reviews the assumptions in the standard test and proposes a novel sample holder for the cone calorimeter which incorporates a large block of aluminium at the rear face of the sample under test. This allows the heat losses at the rear face of the sample to be measured precisely and enables more accurate calculation of the material flammability properties. Tests of PA6 and a nano-composite of PA6 & Cloisite 30B, carried out using the standard and new sample holders, are presented and discussed. The peak of high heat release rate observed in standard tests of PA6 is not observed using the novel sample holder, where the burning behaviour of PA6 and the nano-composite material are largely similar. The implications of these observations are discussed.
Keywords: Cone calorimeter; Flammability; Heat transfer; Nano-composite; Fire retardant;

A novel efficient halogen-free flame retardant system for polycarbonate by Zhi Hu; Li Chen; Bin Zhao; Yuan Luo; De-Yi Wang; Yu-Zhong Wang (320-327).
A novel silicon- and phosphorus-containing flame retardant, poly (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide siloxane), P(DOPO-VTES) was synthesized from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) and vinyltriethoxy silane(VTES). Its chemical structure was confirmed by FTIR. The thermal gravimetrical analysis (TGA) showed that P(DOPO-VTES) had good thermal stability and a high of char yield (86.31%) at 700 °C in nitrogen atmosphere. Its XRD patterns showed that this compound had a certain ordered structure. P(DOPO-VTES) was blended with polycarbonate (PC) together with montmorillonite(MMT) to prepare a series of organic-inorganic hybrids of flame retardant (PC)/P(DOPO-VTES)/MMT via melt blending. The thermal degradation behavior and flame retardancy of those hybrids were investigated with TGA, limiting oxygen index (LOI), vertical burning test (UL-94), and cone calorimeter. The LOI value of the flame-retardant PC systems could reach a maximal value of 32.8 when the content of P(DOPO-VTES) was 5 wt%. When 2 wt% MMT was added into the PC/5%P(DOPO-VTES) system, the UL-94 rating reached V-0. The possible flame retardant mode of MMT was studied via the dynamic rheological properties of the systems and the morphology of the chars remaining after the LOI test and the cone calorimeter test.
Keywords: Polycarbonate; Organic-inorganic hybrid; MMT, flame retardant; Cone calorimeter;

In this work, we report the synthesis and use of an innovative multifunctional radical generator, i.e., bis(1-propyloxy-2,2,6,6-tetramethylpiperidyl)-4-diazene (AZONOR) that alone can effectively provide flame retardancy and self-extinguishing properties to both polypropylene films and plaques. Polypropylene samples containing very low concentrations of 0.25–1 wt% of this additive can successfully pass not only the fire standard tests of DIN 4102 B2 and NF P92-505 but also the more challenging UL94 VTM-2 standard. Besides relative low levels of addition and having no detrimental effect on polypropylene appearance or its mechanical and processing properties another great advantage offered by this flame retardant is its multifunctionality, i.e., high flame retardant durability after artificial weathering. Thus, even after 2000 h of artificial weathering no significant decrease in flame retardant efficacy could be observed.
Keywords: Additives; Flame retardance; Poly(propylene) (PP); HALS;

Incorporation of a flame retardancy enhancing phosphorus-containing diol into poly(butylene terephthalate) via solid state polycondensation: A comparative study by Rafaël Sablong; Robbert Duchateau; Cor E. Koning; Doris Pospiech; Andreas Korwitz; Hartmut Komber; Sandra Starke; Liane Häußler; Dieter Jehnichen; Maria Auf der Landwehr (334-341).
The phosphorus-containing aliphatic-aromatic diol 2-[4-(2-hydroxy-ethoxy)-3-(10-oxo-10-H9-oxa-10-λ5-phospha-phenanthrene-10-yl)-phenoxy]-ethanol, a potential flame retardant, was incorporated into poly(butylene terephthalate) (PBT) by solid state polycondensation. Thus, polymers with various ratios of PBT/DOPO-diol and number-average molar masses up to 57,000 g mol−1 could be prepared. Their molar masses were higher than those of copolyesters with comparable composition obtained by direct melt polycondensation. Structures and properties of copolyesters produced by both methods were not significantly different after melt processing. Their thermal properties and combustion behaviour were investigated by means of DSC, TGA, and pyrolysis combustion flow calorimetry. Combustion studies revealed high char yields, very low heat release capacities and high limiting oxygen index (LOI) at rather low P-contents, indicative of better flame-retardancy properties.
Keywords: Combustion; Halogen-free flame retardancy; PBT; Polycondensation; Solid state transesterification; Thermal properties;

Organohalogen compounds, principally brominated aromatics, continue to be the largest selling flame retardants worldwide. However, there is increasing concern about the bioaccumulation and potential toxicity of these compounds. Consequently, there is great interest in the development of effective alternatives to these materials. Organophosphorus compounds seem to offer the most promise as replacements for halogen-containing flame retardants. One approach to flame-retarding vinyl polymers is to develop reactive monomers containing high levels of phosphorus which may be incorporated directly into the polymer structure. Five phosphorus monomers for use in making fire-retardant copolymers with styrene have been synthesized. A comparative study of the thermal stability of the copolymers has been conducted. Preliminary potential fire behavior data have been obtained using pyrolysis combustion flow calorimetry.
Keywords: Flame retardance; Styrenic; Phosphorus; Phosphate; Phosphonate;

Certain strained five-membered heterocycles undergo thermally-induced, carbon–carbon bond homolysis to generate diradicals capable of initiating vinyl polymerization. These compounds usually contain two oxygen atoms and a larger heteroatom (silicon, phosphorus, sulfur) in addition to carbon. If the heterocycle is suitably substituted with halogen (particularly bromine) containing moities it may function as a vehicle to permit incorporation of flame-retarding units into a polymer or oligomer. When an appropriate heterocycle is used as an initiator for radical polymerization each polymer chain formed contains at least one flame-retarding unit. One such heterocycle is 4,4,5,5-tetra(3,5-dibromophenyl)-2,2-diphenyl-1,3-dioxa-2-silole. In instances in which the heterocycle also acts as a monomer, i.e., it is reactive toward chain-propagating radicals, additional flame-retarding activity may be incorporated into the polymer.
Keywords: 1Silicon-bromine flame retardants; Silole polymerization initiators; Reductive coupling; Thermal stability;

Styrene–butyl acrylate copolymer based fire retardant coatings were prepared using intumescent flame-retardant additives and mineral clay type rheological additives. Three different widely used nanoclays, organic-modified montmorillonite, palygorskite and sepiolite were applied in order to determine their effect on the flame retardancy. Significant differences were found when their heat-shielding activities were evaluated. It was observed that the addition of different clay particles in amount of 0.25 w% changes the char formation process; the height, the morphology, the structure and also the mechanical resistance of the protecting shield. The different geometry and composition of the additives induced different changes in fire performance. In case of palygorskite the catalytic effect of Fe accelerated mainly the thermal decomposition, therefore the fire resistance decreased. The plate-like montmorillonite reduced the extent of the intumescent char, whereas also improved the mechanical and sustained heat resistance of the fire protecting shield. The fibrous sepiolite of low Fe content assisted the development of efficient protecting shield, which exhibited optimal cell structure, suitable thickness, and thus ensured better heat-insulating performance. Consequently, fire retardant effect of sepiolite was found to be better than the other studied clay types.
Keywords: Fire retardancy; Paint; Intumescent coating; Rheological additives; Mineral clay;

An efficiently halogen-free flame-retardant long-glass-fiber-reinforced polypropylene system by Yun Liu; Cheng-Liang Deng; Jing Zhao; Jun-Sheng Wang; Li Chen; Yu-Zhong Wang (363-370).
In order to solve the “candlewick effect” caused by glass fibers, which results in the decrease of flame retardancy of flame-retardant long-glass-fiber-reinforced polypropylene (LGFPP) systems, and the deterioration of mechanical properties caused by adding an additional amount of flame retardants compared with flame-retardant non-glass-fiber-reinforced polypropylene systems so as to keep a same flame retardancy, a novel intumescent flame retardant (IFR) system, which is composed of a charring agent (CA), ammonium polyphosphate (APP) and organically-modified montmorillonite (OMMT), was used to flame retard LGFPP. The thermal stability, combustion behavior, char formation, flame retardant mechanism and mechanical properties of the IFR-LGFPP samples were investigated by thermogravimetric analysis (TGA), limiting oxygen index (LOI), UL-94 test, cone calorimeter test, scanning electronic microscopy, and mechanical property tests. When the content of IFR is 20 wt%, the LOI value of IFR-LGFPP reaches 31.3, and the vertical burning test reaches UL-94 V-0 rating, solving the “candlewick effect” caused by long glass fiber without additional amount of the IFR. All the relevant cone calorimeter parameters also show that IFR-LGFPP has much better flame-retardant behaviors than LGFPP. Furthermore, the mechanical properties of IFR-LGFPP almost remain unchanged in comparison with those of LGFPP containing no IFR. The flame retardant mechanism was also discussed.
Keywords: Flame retardance; Intumescence; Candlewick effect; Long-glass-fiber-reinforced; Polypropylene; Mechanical property;

The applicability of phosphorus-containing reactive amine, which can be used in epoxy resins both as crosslinking agent and as flame retardant, was compared in an aliphatic and an aromatic epoxy resin system. In order to fulfil the strong requirements on mechanical properties of the aircraft and aerospace applications, where they are mostly supposed to be applied, carbon fibre-reinforced composites were prepared. The flame retardant performance was characterized by relevant tests and mass loss type cone calorimeter. Besides the flame retardancy, the tensile and bending characteristics and interlaminar shear strength were evaluated. The intumescence-hindering effect of the fibre reinforcement was overcome by forming a multilayer composite, consisting of reference composite core and intumescent epoxy resin coating layer, which proved to provide simultaneous amelioration of flame retardancy and mechanical properties of epoxy resins.
Keywords: Epoxy resin; Carbon fibre-reinforced composites; Phosphorus-containing reactive amine flame retardant; Effect of flame retardants on mechanical properties;

Almost 50 years ago, the 1950–1960 period witnessed the development of the chemistry underlying most of today’s successful and durable flame retardant treatments for fibres and textiles. In today’s more critical markets in terms of environmental sustainability, chemical toxicological acceptability, performance and cost, many of these are now being questioned. “Are there potential replacements for established, durable formaldehyde-based flame retardants such as those based on tetrakis (hydroxylmethyl) phosphonium salt and alkyl-substituted, N-methylol phosphonopropionamide chemistries for cellulosic textiles?” is an often-asked question. “Can we produce char-forming polyester flame retardants?” and “Can we really produce effective halogen-free replacements for coatings and back-coated textiles?” are others.These questions are addressed initially as a historical review of research undertaken in the second half of the twentieth century which is the basis of most currently available, commercialised flame retardant fibres and textiles. Research reported during the first decade of the twenty first century and which primarily addresses the current issues of environmental sustainability and the search for alternative flame retardant solutions, the need to increase char-forming character in synthetic fibres and the current interest in nanotechnology is critically discussed. The possible roles of micro- and nano-surface treatments of fibre surfaces and their development using techniques such as plasma technology are also reviewed.
Keywords: Flame retardant; Halogen; Phosphorus; Textile; Fibre; Nanotechnology;

Permanent flame retardant finishing of textile materials by a photochemical immobilization of vinyl phosphonic acid by Klaus Opwis; Andreas Wego; Thomas Bahners; Eckhard Schollmeyer (393-395).
A new photochemical method for a permanent flame retardant finishing of textiles made of cotton (CO), polyamide (PA) and polyester (PET) is described. Using a mercury vapour UV lamp vinyl phosphonic acid (VPA) can be fixed durable to different fabrics made of CO, PA and PET in the presence of a cross-linking agent and a photo-initiator. After a home laundering cycle up to 50 wt% of the reaction mixture is retained on the fabrics and the absolute phosphorus content was found to be more than 2.0% in all investigated cases. The photochemically modified textiles showed high levels of flame retardant performance and passed a vertical flammability test for protective clothing.
Keywords: Cotton; Polyamide; Polyester; Photochemical flame retardant finishing; Vinyl phosphonic acid;

Comfortable, flexible upholstery fire barriers on base of bast, wool and thermostable fibres by Ryszard Kozlowski; Muzyczek Malgorzata; Mieleniak Bozena (396-398).
The paper presents elastic barrier materials developed at the INF which play a role of filling and fire barrier material at the same time in upholstery furniture, reducing the development and spread of fire on flammable materials. The presented results of flammability and biophysical tests confirm the comfort of products.The developed barrier materials use natural fibres (wool, flax FR) characterized by good air permeability, hygroscopicity, moisture transport, elimination of electrostatic charges and have effect on climate of interiors also when blended with thermostable fibres such as Polyacrylate. These flexible structures based on blend of natural fibres and thermostable fibres with at least two barrier effects i.e. durable resistance to fire, thermal insulation, control of electrostatic phenomena.
Keywords: Flexible fire barriers; Upholstery non-wovens; Blends of natural and man made fibres; Blends of fibres; Flammability of non-wovens;