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A fully biobased waterborne flame‐retarded epoxy system was prepared using sorbitol polyglycidyl ether epoxy resin (SPE) and phytic acid (PA) as a reactive flame retardant (FR). The flame‐retardant efficiency was evaluated by comparing the reference SPE‐PA system with solventborne and waterborne SPE systems. Additional enhancement of intumescence and reduction of flammability was achieved by incorporating ammonium polyphosphate (APP) and melamine (MEL) into the SPE–PA system. PA, serving as a curing agent, contributed approximately 1% phosphorous content, resulting in an increased limiting oxygen index (LOI). UL‐94 flammability tests demonstrated improved FR properties with PA, and the addition of 2% phosphorous from APP to SPE‐PA achieved a self‐extinguishing V0 UL‐94 rating. Thermogravimetric analysis (TGA) revealed enhanced thermal stability and higher char yield with PA compared with other curing agents. Mass loss calorimetry (MLC) confirmed the superior charring effect of PA compared with other curing agents. The thermal insulation properties of the residual char were assessed by measuring the temperature on the back surface (Tb) of coated steel plates exposed to a 25 kW/m2 heat flux for 1 h. The PA sample containing 3%P of APP exhibited a Tb decrease of 130°C compared with the solventborne reference sample. Scanning electron microscopy analysis of the char morphology supported these findings, indicating the effectiveness of the intumescent FR system. Infrared spectra of the char residues and pyrolysis gaseous products were obtained to gain insights into the flame‐retardant mechanism of the different systems. [ABSTRACT FROM AUTHOR]

Polypropylene (PP) shows no charring ability in burning due to the lack of hydroxyl functional groups; thus, the flame retardant system needs an additional amount of carbonizing agent. An ammonium polyphosphate (APP)-based all-in-one intumescent flame-retardant system was prepared by the in situ polymerization of polymeric methylene diphenyl diisocyanate (pMDI) with a glycerol-based and a glycerol–sorbitol-based polyol of high OH value. The microencapsulated APP with a polyurethane shell (MCAPP) of different polyols was characterized. The MCAPP with speculated improved flame retardant performance was selected for further evaluation in the PP matrix at different loadings by means of standard flammability tests. [ABSTRACT FROM AUTHOR]

A fully waterborne epoxy system was prepared from waterborne sorbitol-based epoxy resin cured with an alkylated polyalkylene polyamine hardener. The flame-retardant property was accomplished by the application of different additive phosphorous flame retardants (FRs). Phosphonate polyol and ethyl ethylene glycol phosphate which are in the liquid phase, and two FRs in the form of fine-grained particles; aluminium diethyl phosphinate (AlPi), ammonium polyphosphate (APP). The flame-retardant epoxy resin blends were prepared at the same levels of phosphorus content. The results are very promising as the self-extinguishing behaviour was observed at 3%P for all the investigated FRs and at 1%P in the case of APP. Limiting oxygen index (LOI) values were practically good for all FRs and extremely improved in the case of APP. LOI was 48% for the APP sample at 3%P content. Furthermore, this blend showed the best results in the forced flaming conditions as the total heat release in cone calorimetry measurements (THR) decreased by 43% and the peak of heat release rate (pHRR) decreased by 65% with more elongated burning compared to the reference SPE matrix. The efficient solid-phase FR effect of APP was confirmed by scanning electron microscopic (SEM) and attenuated total reflection-infrared spectrometry (ATR-IR) analysis of the residual char after cone calorimetry measurements. [ABSTRACT FROM AUTHOR]

The overview of the literature reveals the lack of comprehensive study on the effect of clay minerals in flame-retarded polylactic acid (PLA) composites. This research focuses on sepiolite (SEP) and montmorillonite (MMT) clay minerals and their impact on ammonium polyphosphate (APP)-based intumescent flame-retardant (IFR) system in PLA. The effects of the clay mineral types, their surface modification (O-SEP and O-MMT, respectively) and their concentration in PLA/APP composites on the flame-retardant properties were comprehensively evaluated through thermal and flammability tests. Overall, the sepiolite-containing samples showed the greatest decrease in pHRR and THR values at the 3 m/m% loading level. The sepiolites showed stronger interfacial interactions with the PLA matrix than the montmorillonites, and the organomodification proved to improve the compatibility of both types of clay minerals according to the dynamic mechanical analysis (DMA) results. Yet, the organomodification had a contradictory effect on the flame-retardant properties. In the case of sepiolites, it proved to be beneficial as the O-SEP added composite achieved a 60% decrease in the pHRR value and reduced the THR value to 60%. For montmorillonites, the improved compatibility by the organomodification with the PLA matrix seemed to hinder its flame-retardant effectiveness, as the critical point to its flame-retardant mechanism is the rapid migration and accumulation of the clay minerals towards the surface of the polymer. [ABSTRACT FROM AUTHOR]

Supercritical CO2-assisted extrusion technique was used to produce flame retarded foams from recycled poly(ethylene terephthalate) (rPET). Synergistic combination of aluminium-alkylphosphinate flame retardant (FR) and natural montmorillonite (MMT) was utilised to provide adequate flame retardancy at moderate loadings, i.e. with less than 9% of additives. Addition of FR was found to increase the rate of degradation during production (compounding and foam extrusion), which was effectively compensated by chain extender (CE) addition that ensured the melt strength required to obtain proper foam structure. The effects of the FR content and the CE addition on the viscosity of the rPET compounds and on the morphological, thermal, flammability and mechanical properties of the foam products were comprehensively investigated. When compared to injection moulded bulk materials of identical compositions, the highly porous structure of foams was found to increase flammability according to UL94 tests and LOI measurements but has not been shown to be detrimental to heat release rates as measured by cone calorimetry. It was concluded that with well-balanced composition, i.e. 8% FR + 1% MMT + 1% CE, low-density foams (with porosities higher than 70%) of uniform microcellular structure and prominent flame retardant characteristics (such as V0 rating according to UL94 standard, LOI of 28.5% and by 50% reduced peak of heat release rate and by 30% reduced total heat emission) can be manufactured even from rPET. [ABSTRACT FROM AUTHOR]

A water-soluble sorbitol polyglycidyl ether (SPE) epoxy monomer was cured with a waterborne polyamine hardener to prepare a fully waterborne epoxy system. Aluminum diethyl phosphinate (AlPi) and melamine cyanurate (MC) flame retardants (FRs) were utilized to develop the flame retardancy of this epoxy matrix. The effect of loading different weights of MC with only 1%P-content from AlPi was discussed to investigate the possible cooperative effect of these two FRs. The best results were obtained at 5% MC loading with 1%P of AlPi as the self-extinguishing behavior was observed with a good limiting oxygen index (LOI). Furthermore, under forced flaming conditions in cone calorimetry measurements, the peak of heat release rate (pHRR) decreased by 27.4%, and the total heat release (THR) decreased by 14.5% compared to the reference epoxy system. This enhancement of flame retardant properties might indicate the synergistic effect between MC and AlPi in a waterborne system. [ABSTRACT FROM AUTHOR]

As polypropylene (PP) has no charring ability on its own due to the lack of hydroxyl functional groups, the flame retardant system needs the addition of carbonizing agent in a relatively great amount. Ammonium-polyphosphate (APP), a conventional flame retardant additive was modified by microencapsulation with a sorbitol-based bioepoxy resin shell to create an intumescent flame retardant system with enhanced charring ability for PP. The flame retardant efficiency of the microencapsulated additive, which contains all the components needed in an effective intumescent flame retardant system, was evaluated in PP matrix at different loadings. When compared to the physical mixture of the component, the microencapsuated form of APP (MCAPP) was found to have improved flame retardant efficiency in PP. The LOI values of the MCAPP containing PP samples increased by 8–11 V/V% besides achieved V-0 classification according to the UL94 test. During cone calorimeter tests, the burning intensity was reduced (peak of heat release rate decreased by 20–35% and shifted in time), increased amount of charred residue was obtained, and based on the calculated Flame Retardancy Index (FRI) “Excellent” fire performance was achieved when MCAPP was used. The improved flame retardant performance is attributed to the effective interaction between the APP core and the readily available carbonizing shell, which promoted the formation of increased amount of char accompanied with improved heat protecting and barrier efficiency. [ABSTRACT FROM AUTHOR]

Summary: Flame‐retarded sorbitol‐based bioepoxy resins cured with cycloaliphatic amine hardener and containing different commercially available additive‐type flame retardants (FRs) have been prepared. Three different oxidation states of phosphorus, aluminium diethyl phosphinate (AlPi) (+1), phosphonate polyol (+3), ethyl ethylene glycol phosphate and ammonium polyphosphate (APP) (+5), have been studied. The effect of using melamine cyanurate with APP and AlPi has been assessed. The self‐extinguishing V‐0 rating according to UL‐94 flammability standard tests and very good limiting oxygen index for combustion are displayed for most flame‐retarded samples at 3 wt% phosphorus content. The flame retardancy effect for the additives was confirmed using cone calorimetry. The samples containing MC with APP at 3%P content showed a dramatic reduction of the total heat release by 60% and reduction of the peak of heat release rate by 70% compared to the reference epoxy matrix. The addition of these FRs together did not decrease the glass transition temperature significantly. [ABSTRACT FROM AUTHOR]

The flame retardancy of sorbitol-based epoxy resin is targeted. From the bioepoxy 3% phosphorus-containing matrix samples were prepared. Surprisingly, only HB classification of UL-94 test was reached with the application of ammonium polyphosphate (APP) and resorcinol bis(diphenylphosphate) (RDP). V-0 was reached in the case of red phosphorus (RP) and ammonium salt of DOPO (DXA), while the melamine salt resulted in HB rating, due to the lower P-content of the sample. In the meantime, the highest LOI value was reached in the case of APP. The V-0 red phosphorus composition, however, has an LOI of as low as 25 V/V%. In the case of the thermogravimetric analysis, the application of red phosphorus resulted in significantly increased thermal stability, but faster degradation than in the case of the reference. The RDP showed somewhat decreased stability, due to the less stable phosphorus ester bonds. The amount of the charred residues is increasing with the flame retardant content, but to different extents depending on the type of flame retardant. The highest values were reached with APP. Regarding the cone calorimeter results; the lowest heat release rate belongs to the APP-containing sample, while the V-0 compositions (RP and DXA) show poorer performance in this respect. [ABSTRACT FROM AUTHOR]

Well designed (multilayer, adaptive, reactive) interphases, being a key element of multicomponent structures, could be tailored to different requirements through controlled technologies. This is the link connecting various green, safe, healthy materials and innovative pharmaceuticals. Upgraded recycling could be performed by interfacial consolidation of self-reinforced composites, the flame retardancy of which is feasible with surprisingly low amount of flame retardant. Examples are shown how the reinforced and foamed forms of thermosetting and thermoplastic biopolymers can play a significant role (after flame retardant modification) in the development of airplanes and electric cars. Biopolymer nanofibres, such as polycaprolactone and polyhydroxybutyrate, could be formed with increased productivity for various medical uses. Raman-based control of the units of integrated continuous technologies has been elaborated including controlled formation of crystals with polymer interlayer for direct tableting. [ABSTRACT FROM AUTHOR]

A method was elaborated to prepare flame retarded self-reinforced polypropylene composites by injection moulding. The effect of intumescent flame retardant (FR) loading was comprehensively investigated on the morphology, flammability, and mechanical properties of the self-reinforced polypropylene composites and compared with non-reinforced counterparts of identical additive contents. Homogeneous distribution of both the reinforcing polypropylene fibres and the FR additive was achieved endowing significantly improved strength and stiffness accompanied with increased fire resistance. At 10% FR content, 37% reduction of peak of heat release rate, UL94 V-2 rating, and LOI of 24.5 vol% were achieved without compromising the improved mechanical performance of the injection moulded self-reinforced composites, ie, a 4-fold increase of tensile strength and a 7-fold increase of tensile modulus were reached compared with the non-reinforced counterpart. At higher loading (15% FR), the FR properties improved further (LOI of 29.5 vol% was reached); however, due to the abrasive effect of the FR particles in the matrix, the structure of the reinforcing fibres tends to get damaged during the thermo-mechanical processing, and thus their reinforcing efficacy deteriorated. It is demonstrated that the combination of polymer fibre reinforcement with other fillers (such as FRs) is advantageous and feasible even by injection moulding, but the balance between the individual attributed properties needs to be found. [ABSTRACT FROM AUTHOR]

The flame retardant synergism between highly stretched polymer fibres and intumescent flame retardant systems was investigated in self-reinforced polypropylene composites. It was found that the structure of reinforcement, such as degree of molecular orientation, fibre alignment and weave type, has a particular effect on the fire performance of the intumescent system. As little as 7.2 wt % additive content, one third of the amount needed in non-reinforced polypropylene matrix, was sufficient to reach a UL-94 V-0 rating. The best result was found in self-reinforced polypropylene composites reinforced with unidirectional fibres. In addition to the fire retardant performance, the mechanical properties were also evaluated. The maximum was found at optimal consolidation temperature, while the flame retardant additive in the matrix did not influence the mechanical performance up to the investigated 13 wt % concentration. [ABSTRACT FROM AUTHOR]

Examines the optimum conditions of the monophosphorylation and the monophosphinylation. Kind of phosphate that form a traditional group of organophosphate flame retardants; Functions of the reactive sites of the phosphates and phosphinates.

• Microfibrous structure of HPβCD promotes char formation in PLA/APP system. • Phosphorous silane treatment of HPβCD improves the flame retardant performance. • HPβCD contributes to enhanced physical and chemical interaction between the components. • Improved flame retardancy is provided by thermally stable char. Recently, the flame retardant effectiveness of a 2-hydroxypropyl-β-cyclodextrin (CD) type bio-based carbonising agent has been evinced to noticeably increase when used in a microfibrous form, as obtained by electrospinning method. In the present research, the flame retardant performance of the electrospun CD was further enhanced by reactive surface modification with a phosphorous silane (PSil) compound. Surface-treated and untreated CD-based carbonising agents were compared, both in powder and in microfibrous form, besides ammonium polyphosphate (APP) to form an intumescent flame retardant system for poly(lactic acid) (PLA). The Limiting Oxygen Index (LOI) of the flame-retarded PLA composites increased outstandingly, from 25.0% (corresponding to the 15 wt% APP containing PLA) to as high as 37.5%, as a result of adding only 3 wt% of PSil-treated microfibrous CD to the system. Also, the main combustion characteristics improved; compared to neat PLA, about 50% reduction in the peak heat release rate (pHRR) and 25% reduction in total heat release (THR) were achieved, accompanied by an increased amount of char residue after combustion. The beneficial effect of the PSil-treated CD microfibre relies mainly on its enhanced physical and chemical interaction with APP and its increased charring ability and thermal stability, which contribute to the formation of a fire protecting char of increased structural integrity. [ABSTRACT FROM AUTHOR]

• HP-β-CD microfibers were prepared by high throughput aqueous HSES technology. • Microfibrous HP-β-CD enhances char formation in intumescent flame retarded PLA. • Improved fire retardancy is provided by thermally and mechanically resistant char. 2-hydroxypropyl-β-cyclodextrin (HP-β-CD) microfibres with diameters ranging between 3 and 7 µm were prepared by aqueous solution based high-speed electrospinning (HSES) technique and then used as carbonising agent at 3 wt% loading besides 15 wt% ammonium polyphosphate (APP) to obtain flame-retarded poly(lactic acid) (PLA) composites. The high specific surface area of the microfibrous HP-β-CD was found to have a crucial role in its flame retardant efficiency. Compared to the effect of the same amount of conventional HP-β-CD powder additive, microfibrous HP-β-CD resulted in higher char yields both during thermogravimetric analysis and cone calorimeter test accompanied with significantly increased mechanical resistance and consequently with improved flame retarding efficacy. The Limiting Oxygen Index (LOI) of the intumescent flame-retarded PLA composite increased noticeably, from 29.0% to 32.5%, while the Flame Retardancy Index (FRI), determined from cone calorimetry data, increased from 1.9 (with powder HP-β-CD) to 2.6 (with microfibrous HP-β-CD) only by changing the physical form i.e. the specific surface area of the used HP-β-CD. The advantage of the special microfibrous structure of the oligosaccharide type charring agent lies in the efficient interaction with APP and the attribution of the intumescent char layer with improved thermal and mechanical resistance without compromising its swelling ability. Besides, the microfibrous structure of the HP-β-CD also contributed to the improvement of the mechanical performance of the flame retarded PLA composites. [ABSTRACT FROM AUTHOR]

Flame-retardant-treated cellulose (FR-cell) was used as bio-based charring agent in combination with ammonium polyphosphate (APP) based intumescent flame retardant (IFR) system to reduce the flammability of poly(lactic acid) (PLA) foams produced by supercritical carbon dioxide (sc-CO 2 ) assisted extrusion. FR-cell was obtained by surface treatment of cellulose with diammonium phosphate (DAP) and boric acid (BA). To enhance foamability, the inherently low melt strength and slow crystallization rate of PLA was increased by adding epoxy-based chain extender (CE) and montmorillonite (MMT) nanoclay, respectively. The morphology of the foams was examined using water displacement method, scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS). Thermal properties were assessed using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Flammability was evaluated by limiting oxygen index (LOI) measurements, UL-94 tests and pyrolysis combustion flow calorimetry (PCFC). The continuous extrusion foaming technique allowed the preparation of low density PLA foams with uniform microcellular structure and void fractions higher than 90% accompanied with increased crystallinity of up to 19%. Despite the high expansion ratios (i.e. high surface area), the PLA foams showed excellent flame retardancy, UL-94 V-0 rate and LOI value of 31.5 vol% was achieved with an additive content as small as 19.5%. However, the flame retardant synergism evinced between IFR and MMT proved to be less pronounced in the expanded foams compared to bulk materials with identical additive contents. [ABSTRACT FROM AUTHOR]

Abstract: Multilayered self-reinforced composites were developed from a density-separated light fraction of automotive shredder waste of high polyolefin content, which can fulfil the current technical, safety and environmental requirements of structural materials. The significantly enhanced mechanical properties of the recycled composites were ensured by polypropylene fabric reinforcement; meanwhile, reduced flammability was obtained by modifying the matrix layers, made of secondary raw materials, with phosphorous-containing flame retardant additive. The results of the new flame retarded composite systems allowed the discussion of a novel mechanistic observation. The mechanical and flammability properties of the prepared self-reinforced composites are compared to conventional glass fabric reinforced composites and to compounds without reinforcement. [Copyright &y& Elsevier]