Preparation,thermal, and flammability of halogen‐free flame retarding thermoplastic poly(ether‐ester) elastomer/montmorillonite nanocomposites

In this article, the nanocomposites thermoplastic polyester‐ether elastomer (TPEE) with phosphorous–nitrogen (P–N) flame retardants and montmorillonite (MMT) was prepared by melt blending.The fire resistance of nanocomposites was analyzed by limiting oxygen index (LOI) and vertical burning (UL94) test. The result shows that the flame retardants containing P–N increased the LOI of the material from 17.3 to 27%. However, TPEE containing P–N flame retardants just got UL94 V‐2 ranking, which resulted in the flaming dripping phenomenon. On the other hand, TPEE containing P–N flame retardant and organic‐modified montmorillonite (o‐MMT) achieved UL94 V‐0 rating for the special microstructure. The XRD and TEM morphology has demonstrated that the formation of multi‐ordered structure regarding restricted segmental motions at the organic–inorganic interface and stronger interactions between the clay mineral layers and the polymer chains. The structure was supported by the results of rheological properties and DSC analysis. The thermal degradation and char residue characterization was studied by thermal gravimetric analysis (TGA) and SEM‐EDX measurements, respectively. The TGA and SEM‐EDX have demonstrated that o‐MMT results in the increase of char yield and the formation of the thermal stable carbonaceous char. POLYM. COMPOS., 37:700–708, 2016. © 2014 Society of Plastics Engineers     

Phosphorus‐containing thermoplastic poly(ether ester) elastomers showing intrinsic flame retardancy

A series of poly(ether ester) thermoplastic elastomers (TPEEs) are synthesized by a one‐pot, two‐step method: (1) transesterification of dimethyl‐2,6‐naphthalenedicarboxylate with 1,4‐butanediol (BDO) as chain extender (CE), followed by (2) low‐pressure melt polycondensation with poly(tetramethylene ether glycol) as a soft segment in the presence of Ti(OBu)₄ as a catalyst. In order to design phosphorous‐containing flame‐retardant TPEEs, hydroxyl‐terminated isobutylbis(hydroxypropyl)phosphine oxide (IHPO) is integrated into the polymer backbone as the second CE, modulating the IHPO content up to 30% with respect to BDO. The resultant TPEEs are systematically characterized using various spectral, thermal, and mechanical analyses. An increase in phosphorus content in the polymer backbone enhances the flame retardancy of TPEE, adapting them as promising halogen‐free self‐extinguishing thermoplastic elastomers without losing their elastomeric properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45478.     

Synergistic effects of hydroxides and dimethyl methylphosphonate on rigid halogen‐free and flame‐retarding polyurethane foams

Rigid halogen‐free and flame‐retarding polyurethane foams are prepared with aluminum hydroxide, brucite, and DMMP. The effects of the hydroxides and DMMP on the foaming process and flame retarding properties of the foams are investigated by thermo gravimetric analysis, limiting oxygen index, and X‐ray powder diffraction. The thermal stability of the rigid polyurethane foams is close to that of the hydroxide fillers, with aluminum hydroxide providing better flammability performance than brucite. The hydroxide fillers and DMMP play a synergistic role in the rigid polyurethane foams and the limiting oxygen indices are up to 28.4% and 32.4%, respectively. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Development of halogen‐free flame‐retardant thermoplastic elastomer polymer blend

Ethylene‐propylene diene rubber (EPDM) and isotactic polypropylene (iPP) blends have widest industrial applications that require a degree of flame retardancy. Halogen‐free intumescent technology based on phosphorous salt is a significantly advanced approach to make the polymer flame‐retardant. Both ammonium polyphosphate and ethylenediamine phosphate are important intumescent compounds. Their combination with carbonific and spumific agents were studied in binary blends of EPDM/PP. The polymer system was vulcanized online during melt mixing. Intumescent flame‐retardant polymer systems exhibit good flame‐retardancy with optimum comparable physiomechanical, electrical, and fluid resistance properties, including lower smoke emission, which is essential to protect people because the visibility remains unaffected in the event of fire. Pronounced charring and intumescent effect appear to enhance the flame‐retardancy of the polymers. Possible expected intumescent mechanism is proposed based on the nonpyrolysis mechanism for the flame‐retarded polymer and the intumescent components. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 407–415, 2004     

Rheological and fire properties of a composite of unsaturated polyester resin and halogen‐free flame retardants

The main subject of the present research is to determine the impact of flame retarding fillers on macroscopic properties of composites. The effect on rheological properties of composition unsaturated polyester resin (UP) and flame retardant blend (FR) consisting of expandable graphite (EG) and or not modified silica and: (1) melamine polyphosphate (MPP) with ammonium polyphosphate (APP), (2) MPP with aluminum trihydrate (ATH), (3) only MPP was examined. Next, their influence on thixotropic properties of UP was estimated. FR fillers were compared according to their grain size, specific surface, and shape factor. Rheological properties were determined by applying hysteresis loop surface and thixotropy factor measuring. For the UP + FR composition, the dependence of grain morphological parameters, such as shape factor and specific surface, on viscosity and hysteresis loop surface was determined experimentally. All of the tested composites consisting of UP + 40% FR blend exhibits high flame resistance. An addition of only 2% of modified silica to all of the FR blends caused significant enlargement of hysteresis loop surface and thixotropy index. Hence, for the next stage of the research (an industrial test of GRP pipes casted by the centrifugal method) FR blend without modified silica was chosen. A composite consisting of UP, MP, APP and EG is characterized by lower heat release rate (HRR_max) (ca. 83%) and lower TSR (ca. 80%), ALMR (55%), and MARHE (73%) in comparison to UP resin; and that UP + FR composition exhibit satisfactory rheological properties as well. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44371.     

Synthesis and flammability testing of epoxy functionalized phosphorous‐based flame retardants

Several potential new phosphorus‐containing flame retardant molecules were evaluated for heat release reduction potential by incorporation of the molecules into a polyurethane, generated from methylene diphenyl diisocyanate and 1,3‐propane diol. The heat release reduction potential of these substances was evaluated using the pyrolysis combustion flow calorimeter (PCFC). The polyurethanes were prepared in the presence of the potential flame retardants via solvent mixing and copolymerization methods to qualitatively evaluate their potential reactivity into the polyurethane prior to heat release testing. The functionality of the flame retardants was epoxide based that would potentially react with the diol during polyurethane synthesis. Flammability testing via PCFC showed that the heat release reduction potential of each of the flame retardants was structure dependent, with phosphates tending to show more effectiveness than phosphonates in this study, and alkyl functionalized phosphorus groups (phosphate or phosphonate) being more effective at heat release reduction than cyclic functionalized groups. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42296.     

Synergistic effect of metal oxides on the flame retardancy and thermal degradation of novel intumescent flame‐retardant thermoplastic polyurethanes

The synergistic effects of some metal oxides on novel intumescent flame retardant (IFR)–thermoplastic polyurethane (TPU) composites were evaluated by limiting oxygen index (LOI), vertical burning test (UL‐94), thermogravimetric analysis (TGA), cone calorimetry, and scanning electron microscopy. The experimental data indicated that the metal oxides enhanced the LOI value and restricted the dropping of the composites. The IFR–TPU composites passed the UL‐94 V‐0 rating test (1.6 mm) in the presence of magnesium oxide (MgO) and ferric oxide (Fe₂O₃) at 35 wt % IFR loading, whereas only the MgO‐containing IFR–TPU composite reached a UL‐94 V‐0 rating at 30 wt % IFR loading. The TGA results show that the metal oxides had different effects on the process of thermal degradation of the IFR–TPU compositions. MgO easily reacted with polyphosphoric acid generated by the decomposition of ammonium polyphosphate (APP) to produce magnesium phosphate. MgO and Fe₂O₃ showed low flammability and smoke emission due to peak heat release rate, peak smoke production rate, total heat release, and total smoke production (TSP). However, zinc oxide brought an increase in the smoke production rate and TSP values. Among the metal oxides, MgO provided an impressive promotion on the LOI value. The alkaline metal oxide MgO more easily reacted with APP in IFRs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Reactive,intumescent, halogen‐free flame retardant for polypropylene

A reactive, intumescent, halogen‐free flame retardant, 2‐({9‐[(4,6‐diamino‐1,3,5‐triazin‐2‐yl)amino]‐3,9‐dioxido‐2,4,8,10‐tetraoxa‐3,9‐diphosphaspiro[5.5]undecan‐3‐yl}oxy)ethyl methacrylate (EADP), was synthesized through a simple three‐step reaction from phosphorus oxychloride, pentaerythritol, hydroxyethyl methacrylate, and melamine. EADP exhibited excellent thermal stability and char‐forming ability, as revealed by thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The TGA results show that the temperature at 5% weight loss was 297.8°C and the char yield at 700°C was 51.75%. SEM observation revealed that the char showed a continuous and compact surface and a cellular inner structure with different sizes. Composite of polypropylene (PP) with a 25 wt % addition of EADP (PP/EADP25) passed the UL‐94 V‐0 rating and showed a limiting oxygen index value of 31.5. Compared with those of neat PP, the flexural strength and modulus values of PP/EADP25 were somewhat improved, the tensile strength was basically unchanged, and the notched Izod impact strength was slightly decreased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40054.     

Structure−property relationships of halogen‐free flame‐retarded poly(butylene terephthalate) and glass fiber reinforced PBT

Flame retardancy for thermoplastics is a challenging task where chemists and engineers work together to find solutions to improve the burning behavior without strongly influencing other key properties of the material. In this work, the halogen‐free additives aluminum diethylphosphinate (AlPi‐Et) and a mixture of aluminum phosphinate (AlPi) and resorcinol‐bis(di‐2,6‐xylyl phosphate) (AlPi‐H + RXP) are employed in neat and reinforced poly(butylene terephthalate) (PBT), and the morphology, mechanical performance, rheological behavior, and flammability of these materials are compared. Both additives show submicron dimensions but differ in terms of particle and agglomerate sizes und shapes. The overall mechanical performance of the PBT flame‐retarded with AlPi‐Et is lower than that with AlPi‐H‐RXP, due to the presence of larger agglomerates. Moreover, the flow behavior of the AlPi‐Et/PBT materials is dramatically changed as the larger rod‐like primary particles build a percolation threshold. In terms of flammability, both additives perform similar in the UL 94 test and under forced‐flaming combustion. Nevertheless, AlPi‐Et performs better than AlPi‐H + RXP in the LOI test. The concentration required to achieve acceptable flame retardancy ranges above 15 wt %. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and properties of halogen‐free flame‐retarded phthalonitrile–epoxy blends

Halogen‐free flame‐retarded blends composed of 2,2‐bis[4‐(3,4‐dicyanophenoxy) phenyl] propane (BAPh) and epoxy resin E‐44 (EP) were successfully prepared with 4,4′‐diaminodiphenyl sulfone as a curing additive. The structure of the copolymers was characterized by Fourier transform infrared spectroscopy, which showed that epoxy groups, a phthalocyanine ring, and a triazine ring existed. The limiting oxygen index values were over 30, and the UL‐94 rating reached V‐0 for the 20 : 80 (w/w) BAPh/EP copolymers. Differential scanning calorimetry and dynamic rheological analysis were employed to study the curing reaction behaviors of the phthalonitrile/epoxy blends. Also, the gelation time was shortened to 3 min when the prepolymerization temperature was 190°C. Thermogravimetric analysis showed that the thermal decomposition of the phthalonitrile/epoxy copolymers significantly improved with increasing BAPh content. The flexible strength of the 20:80 copolymers reached 149.5 MPa, which enhanced by 40 MPa compared to pure EP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal and flame‐retardant properties of polyester fabric grafted with polyanilines

The chemical grafting of polyaniline, poly(o‐anisidine), and poly(o‐toluidine) on polyester fabric was carried out with ammonium peroxodisulfate in an acidic medium. The formation of the grafted fabric substrate was confirmed with reflectance spectroscopy, Fourier transform infrared spectroscopy, weight‐loss studies, and conductivity measurements. The grafting percentage and efficiency percentage were determined for the different grafted substrates. The thermal and flame‐retardant properties of these grafted substrates were elucidated. Thermogravimetric analysis thermograms and derivative thermogravimetry curves showed that the grafted substrates had a higher thermal stability and char‐residue percentage at 700°C. The grafted substrates showed a higher activation energy of thermal decomposition than the nongrafted substrates. The grafted substrates showed good flame retardancy, which was evident from the increase in the limited oxygen index in comparison with that of the nongrafted substrate. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1981–1988, 2004     

Flame‐retardant and morphological analysis of nitrogen heterocycle‐modified poly(vinyl alcohol) and their application for adsorption of heavy metal ions

The functional modification of poly (vinyl alcohol) (PVA) was conducted through phosphorus containing nitrogen heterocycles. This has been believed to have extensive thermal stability and heavy metal ion adsorption in the area of polymers. The heterocyclic modified polymers were characterized by Infra red (FTIR), Nuclear magnetic resonance spectroscopy, and elemental analysis. Thermogravimetric analysis studies displayed that phosphorus‐containing five membered and fused heterocyclic based PVA were less thermally stable than six membered compounds. Differential scanning calorimetric studies reported that the glass transition and melting point temperature of the heterocyclic modified PVA was higher than the pure PVA. X‐ray diffraction studies were done to analyze the structure of the modified polymer. Atomic force microscopy surface scans showed that the modified polymeric surface was found to have rough in micrometer scale. Modified PVA showed improved thermal stability, flame retardance, organosolubility, and surface roughness. The adsorption capacities of the modified PVA were determined for several heavy metal ions with the variation of pH. The adsorption capacity was found as 289 mg Pd²⁺/g of imidazole modified PVA and exhibited higher than other modified PVA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation,characterization and properties of a halogen‐free phosphorous flame‐retarded poly(butylene terephthalate) composite based on a DOPO derivative

A phosphorous flame retardant (DOPO‐MAH) was synthesized through the reaction between of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) and maleic anhydride (MAH) and confirmed by FT‐IR, ¹H NMR, and ³¹P NMR techniques. The obtained flame retardant was then melt blended with poly(butylene terephthalate) (PBT) to prepare flame retardant PBT/DOPO‐MAH composites. The composites were characterized by LOI, UL‐94, and mechanical tests as well as scanning electron microscopy, thermogravimetric analysis, and differential scanning calorimetry analysis. On adding 20 wt % DOPO‐MAH, LOI increased from 20.9 to 25.7 and the UL‐94 V‐0 rating was achieved, whereas the tensile and flexural properties were notably improved. Torque‐time profile during the melt blending and intrinsic viscosity of the composite indicated that DOPO‐MAH acted as both flame retardant and chain extender for the PBT matrix. The results showed that PBT/DOPO‐MAH composite is a promising material for its good comprehensive properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1301‐1307, 2013     

Flame‐retardant and thermal degradation mechanism of low‐density polyethylene modified with aluminum hypophosphite and microencapsulated red phosphorus

Aluminum hypophosphite (AHP), a novel flame retardant, was used to improve the flame retardancy of low‐density polyethylene (LDPE) with microencapsulated red phosphorus (MRP). The synergistic effect between MRP and AHP was investigated by the limiting oxygen index (LOI), vertical burning test (UL‐94), and thermogravimetric analysis. When the contents of MRP and AHP were 10 and 30 phr, the LOI of LDPE/10MRP/30AHP composite was 25.5%, and it passed the UL‐94 V‐0 rating (the number before “MRP” and “AHP” is the loading of MRP and AHP, In LDPE/10MRP/30AHP, the content of the LDPE, MRP and AHP is 100phr, 10phr and 30phr, where phr refers to parts per hundreds of resin). The results of cone calorimetry testing show that the heat release rate of the composites was significantly reduced, and the strength of the char layer improved when the loading of AHP increased. The thermal stability of the LDPE/10MRP/30AHP composite was enhanced. The structure of the char was investigated by Fourier transform infrared spectrometry and scanning electron microscopy/energy‐dispersive spectrometry. The results indicate that AHP promoted the formation of stable char. This research provided a good way to prepare flame‐retardant materials with a halogen‐free flame retardant and contributed to environmental protection. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43225.     

Effect of zinc oxide on properties of phenolic foams/halogen‐free flame retardant system

A halogen‐free flame retardant system consisting of ammonium polyphosphate (APP) as an acid source, blowing agent, pentaerythritol (PER) as a carbonific agent and zinc oxide (ZnO) as a synergistic agent, was used in this work to enhance flame retardancy of phenolic foams. ZnO was incorporated into flame retardant formulation at different concentrations to investigate the flammability of flame retardant composite phenolic foams (FRCPFs). The synergistic effects of ZnO on FRCPFs were evaluated by limited oxygen index (LOI), thermogravimetric analysis (TGA), cone calorimeter tests, and images of residues. Results showed that the flame retardant significantly increased the LOI of FRCPFs. Compared with PF, heat release rate (HRR), total heat release (THR), effective heat of combustion (EHC), production or yield of carbon monoxide (COP or COY) and Oxygen consumption (O₂C) of FRCPFs all remarkably decreased. However specific extinction area (SEA) and total smoke release (TSR) significantly increased, which agreed with the gas‐phase flame retardancy mechanism of the flame retardant system. The results indicated that FRCPFs have excellent fire‐retardant performance and less smoke release. And the bending and compression strength were decreased gradually with the increase of ZnO. The comprehensive properties of FRCPFs were better when the amount of ZnO was 1～1.5%. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42730.     

Thermal degradation and combustion behavior of intumescent flame‐retardant polypropylene with novel phosphorus‐based flame retardants

The objective of this study was to develop an environmentally friendly fire‐retardant polypropylene (PP) with significantly improved fire‐retardancy performance with a novel flame‐retardant (FR) system. The system was composed of ammonium polyphosphate (APP), melamine (MEL), and novel phosphorus‐based FRs. Because of the synergistic FR effects among the three FRs, the FR PP composites achieved a V‐0 classification, and the limiting oxygen index reached as high as 36.5%. In the cone calorimeter test, both the peak heat‐release rate (pHRR) and total heat release (THR) of the FR PP composites were remarkably reduced by the incorporation of the novel FR system. The FR mechanism of the MEL–APP–FR–PP composites was investigated through thermogravimetric analysis and char residue characterization, and the results reveal that the addition of MEL–APP–FRs promoted the formation of stable intumescent char layers. This led to the reduction of pHRR and THR and resulted in the improvement of the fire retardancy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45962.     

Halogen‐free flame‐retardant waterborne polyurethane with a novel cyclic structure of phosphorus−nitrogen synergistic flame retardant

A novel phosphorus?nitrogen flame retardant, octahydro‐2,7‐di(N,N‐dimethylamino)‐1,6,3,8,2,7‐dioxadiazadiphosphecine (ODDP), with bi‐phosphonyl in a cyclic compound, was synthesized by the reaction of POCl₃, NH(CH₃)₂·HCl with OHCH₂CH₂NH₂ in CH₂Cl₂ solution, and characterized by Fourier transform infrared spectrometer, nuclear magnetic resonance, and mass spectrum. ODDP has been successfully reacted with polyurethane (PU) as a chain extender to prepare phosphorus–nitrogen synergistic halogen‐free flame‐retardant waterborne PU (DPWPU). Limiting oxygen index (LOI), UL‐94, thermogravimetric analysis and scanning electron microscopy suggest the excellent flame retardancy of the DPWPU polymer. When the content of ODDP was 15 wt %, the LOI of DPWPU was 30.6% and UL‐94 achieved a V‐0 classification. Compared with the unmodified WPU, the thermodecomposition temperature of the DPWPU was reduced and the amount of carbon residue was increased to 18.18%. The surface of carbon residue was shown to be compact and smooth without holes, which would be favorable for resisting oxygen and heat. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41288.     

Investigations of thermal degradation behavior and fire performance of halogen‐free flame retardant poly(1,4‐butylene terephthalate) composites

This work aims to develop halogen‐free poly(1,4‐butylene terephthalate) (PBT) composites with enhanced flame retardancy using ecofriendly flame retardants, aluminum hypophosphite (AHP) and melamine derivatives (melamine polyphosphate and melamine cyanurate). Microscale combustion calorimetry and thermal gravimetric analysis/infrared spectrometry (TG‐IR) technique were used to investigate the potential fire hazards of these PBT composites. For the PBT composites with the incorporation of AHP and melamine derivatives, the heat release capacity (HRC) which is an indicator of a material fire hazard was significantly reduced, and the intensities of a variety of combustible or toxic gases detected by TG‐IR technique were remarkably decreased. Moreover, a loading of 20 wt % flame retardant mixture fulfilled the PBT composites high limited oxygen index (LOI) and V‐0 classification in UL 94 testing. An intumescent flame retarded mechanism was speculated in this work, because numerous bubble‐like char residues were found on the surface of the samples containing flame retardant mixture after LOI testing. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Expandable graphite systems for halogen‐free flame‐retarding of polyolefins. II. Structures of intumescent char and flame‐retardant mechanism

The structures of the intumescent charred layers formed from polyolefin (PO) blends with expandable graphite (EG) and/or the other free‐halogen flame retardant (HFFR) and their flame‐retardant mechanism were studied by Fourier transform infrared (FTIR) spectroscopy, X‐ray photoelectron spectroscopy (XPS), laser Raman spectroscopy (LRS), scanning electron microscopy (SEM), differential thermal analysis (DTA), and thermal conductivity (TC) measurements. The FTIR, XPS, and LRS data showed that the carbonaceous structures of intumescent charred layers consist of EG and various numbers of condensed benzene rings and/or phosphocarbonaceous complexes attached by the P—O—C and P—N bonds or quaternary nitrogen or dehydrated zinc borate (ZB). These results and the morphologic structures observed by SEM have demonstrated that the compact structures of charred layers slow down heat and mass transfer between the gas and condensed phase and prevent the underlying polymeric substrate from further attack by heat flux in a flame. The DTA data provide the positive evidence for the flame‐retardant mechanism of the PO/EG/HFFR systems, which works by increasing the oxidation temperature and decreasing thermal oxidation heat. At the same time, the TC data reveal the flame‐retardant essence of the charred layers as good heat‐insulated materials whose TC value is only about 1/10 of the corresponding blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1190–1197, 2001     

Mechanism of action of different d‐spacings clays on the intumescent fire retardance of polymers

A series of sodic and organophilic clays with different d‐spacings was added to a polymeric matrix of poly (ethylene‐co‐butyl acrylate) EBA‐30, containing an intumescent formulation of ammonium polyphosphate (APP) and pentaerythritol (PER), in order to investigate the influence of the d‐spacings of the clays on their synergistic effects with the intumescent formulation. A series of samples was evaluated through cone calorimetry, SEM, TG‐FTIR, FTIR, and XRD of burned residues. The results revealed that the addition of clays with smaller d‐spacings led to a synergistic interaction with the intumescent formulation, and consequently to an improvement in the flame retardance of the materials. This effect was not observed with the addition of clays with d‐spacings larger than 30 Å. For these materials, the formation of a less homogeneous and structured intumescent layer, and a delay in the formation of the phosphocarbonaceous species which act as char precursors was observed. This delay could be responsible for the loss of synergy and also for the type of char morphology formed when larger d‐spacings clays were used. XRD analyses results indicated that the presence of clays in the materials promoted changes in the crystalline phase of the char when the samples were submitted to higher temperatures. Those changes probably allowed for the maintenance of the structures at high temperatures. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1759–1771, 2013