Flammability and combustion properties of ammonium polyphosphate-/poly(acrylic acid)- based layer by layer architectures deposited on cotton,polyester and their blends

Layer by layer architectures consisting of four layer repetitive unit (QL) based on poly(diallydimethylammonium chloride)/poly(acrylic acid)/poly(diallydimethylammonium chloride)/ammonium polyphosphate have been deposited on cotton, polyester and their blends in order to promote the formation of an aromatic and stable carbonaceous structure (char) during combustion. The LbL-treated fabrics have been subjected to flammability (reaction to flame application) and combustion (reaction to different external heat fluxes) tests. The coatings were able to remarkably enhance the char formation of each substrate just after 1QL deposition; furthermore, 5 and 10QL assemblies have favoured the formation of intumescent-like structures with further improvement of the final residue. As a consequence, the treated fabrics have shown a strong reduction of the flammability (afterglow and incandescent melt dripping suppression) and combustion (reduced heat released). Infrared spectroscopy has pointed out the aromatic nature of the residues left after the combustion.     

The role of pre-hydrolysis on multi step sol–gel processes for enhancing the flame retardancy of cotton

The flame retardancy properties of cotton have been enhanced by exploiting an optimized multistep sol–gel process, consisting of a pre-hydrolysis step, followed by consecutive depositions of hybrid phosphorus-doped silica layers, using DPTS as precursor of the oxidic phases. Upon optimization, it has been demonstrated that just one phosphorus-doped silica layer is able to strongly reduce the heat release rate (?52 %), and the total smoke release (?56 %) and its rate (?62 %) with respect to the untreated fabric. In addition, the deposition of three layers allows achieving a higher flammability resistance if compared to a single layer, as indicated by the final residue after the flammability tests. As far as flammability resistance is concerned, the new coatings have shown a good durability when subjected up to five washing cycles according to ISO 6330 standard.     

Synergistic effects of cerium phosphate and intumescent flame retardant on EPDM/PP composites

An intumescent flame retardant system composed of ammonium polyphosphate (APP) and pentaerythritol (PER) was used for flame retarding ethylene–propylene–diene‐modified elastomer (EPDM)/polypropylene (PP) blends. Cerium phosphate (CeP) was synthesized and the effect on flame retardancy and thermal stability of EPDM/PP composites based on intumescent flame retardant (IFR) were studied by limiting oxygen index (LOI), UL‐94, and thermogravimetic analysis (TGA), respectively. Scanning electron microscopy (SEM) and Fourier transform infrared spectrometry (FTIR) were used to analyze the morphological structure and the component of the residue chars formed from the EPDM/PP composites, and the mechanical properties of the materials were also studied. The addition of CeP to the EPDM/PP/APP/PER composites gives better flame retardancy than that of EPDM/PP/APP/PER composites. TGA and RT‐FTIR studies indicated that an interaction occurs among APP, PER, and EPDM/PP. The incorporation of CeP improved the mechanical properties of the materials. Copyright © 2010 John Wiley & Sons, Ltd.     

Synergistic effect of combined dimethyl methylphosphonate with aluminum hydroxide or ammonium polyphosphate retardant systems on the flame retardancy and thermal properties of unsaturated polyester resin

A series of flame-retardant unsaturated polyester resin (UPR) were prepared by the addition of dimethyl methylphosphonate (DMMP) with various amounts of aluminum hydroxide (ATH) or ammonium polyphosphate (APP) as the flame retardants. The combustion resistance effects of ATH/DMMP and APP/DMMP systems were evaluated by limiting oxygen index test and vertical burning test (UL-94). The thermal properties of UPR were investigated by thermogravimetric analysis. The structure of char was observed by scanning electron microscopy. DMMP incorporated with ATH or APP improved the flame retardancy and thermal properties of UPR. However, the fire-retardant mechanism of these two systems were different: The ATH/DMMP system provided synergistic effect in charring property of the UPR, produced great amount of residual char, and thus revealed the excellent flame retardancy. The APP/DMMP system further improved the flame retardancy of the UPR due to the change in the residual char structure rather than the increase in the production of char.     

Synthesis of novel poly(aminophosphonate ester)s flame retardants and their applications in EVA copolymer

Novel oligomeric intumescent flame retardants, poly(amino phosphonate ester)s (PAPEs), containing both phosphorous and nitrogen, were synthesized by reacting diethyl phosphite with two different polyschiff bases obtained from the reaction of diamines with dialdehyde. The target PAPEs (designated as PAPE‐d and PAPE‐e, respectively) were characterized by ¹H NMR, ³¹P NMR, Fourier Transform infrared spectroscopy, elemental analysis, gel permeation chromatography and thermogravimetric analysis (TGA) techniques. Thermal stability and flammability of ethylene‐vinyl acetate copolymer (EVA)/PAPE blends with various PAPE content were investigated by TGA, limited oxygen index (LOI), vertical burning test (UL‐94) and microscale combustion colorimeter (MCC). The results indicate that PAPEs effectively improve the flame retardancy of EVA. The EVA/30%PAPE‐e blend has a LOI value of 28, and its peak heat release rate (PHRR) value in MCC measurement is reduced by 36%. At the same time, the EVA/PAPE blends also have high yield of residual char, indicating that PAPEs are effective charring agents. Scanning electron microscopy observations of the residues of the EVA/PAPE blends show the existence of compact char layer on the surface of the residues, which is responsible for the improvement of the flame retardancy of EVA. Copyright © 2012 John Wiley & Sons, Ltd.     

Synergistic effects of ammonium polyphosphate and red phosphorus with expandable graphite on flammability and thermal properties of HDPE/EVA blends

In this work, the flame‐retardant high‐density polyethylene/ethylene vinyl‐acetate copolymer (HDPE/EVA) composites have been prepared by using expandable graphite (EG) as a flame retardant combined with ammonium polyphosphate (APP) and red phosphorus masterbatch (RPM) as synergists. The synergistic effects of these additives on the flammability behaviors of the filled composites have been investigated by limiting oxygen index, UL‐94 test, cone calorimeter test, thermogravimetric analysis (TGA), Fourier‐transform infrared (FTIR), and scanning electron microscopy. The results show that APP and RPM are good synergists for improving the flame retardancy of EG‐filled HDPE/EVA composites. The data from TGA and FTIR spectra also indicate the synergistic effects of APP and RPM with EG considerably enhance the thermal degradation temperatures but decrease the charred residues of the HDPE/EVA/EG composites because the flame‐retardant mechanism has changed. The morphological observations present positive evidences that the synergistic effects take place in APP and RPM with EG in flame‐retardant EG‐filled HDPE/EVA/EG composites. The formation of stable and compact charred residues promoted by APP and RPM with EG acts as effective heat barriers and thermal insulations, which improves the flame‐retardant performances and prevents the underlying polymer materials from burning. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of ammonium polyphosphate and fillers on flame retardant and mechanical properties of recycled PET injection molded

Ammonium polyphosphate (APP) and inorganic fillers were applied for improving flame retardancy and mechanical performance of recycled poly(ethylene terephthalate) (RPET). RPET was compounded with 5–10 wt% of talc and glass bead using twin screw extruder then were injection molded with 2 wt% of APP. The effects of fillers contents and APP on properties and flame retardancy of RPET composites were investigated. The incorporation of talc and glass bead as well as the adding of APP significantly improved tensile and flexural modulus of RPET composites. Scanning electron microscope micrographs indicated good distribution of talc, while glass bead was agglomerated on the RPET matrix. Flame‐retardant property of neat RPET and the RPET composites revealed V‐2 of UL‐94 flammability rating. It can be noted that the composites were less dripping because of the synergistic effect of adding talc and glass bead with APP. From thermogravimetric analysis results, larger of residual char contents and lower values of the activation energy were considered for enhancing flame retardancy in the RPET composites. Copyright © 2015 John Wiley & Sons, Ltd.     

双层包裹聚磷酸铵微胶囊合成及其在环氧树脂中阻燃研究

采用原位聚合法制备了蜜胺树脂(MF)和环氧树脂(EP)双层包裹聚磷酸铵(APP),得到一种新型核壳结构的微胶囊阻燃剂(EMFAPP).用傅里叶红外光谱(FTIR)和扫描电镜(SEM)对微胶囊的核壳结构进行了表征;用极限氧指数(LOI)、垂直燃烧等级测试(UL 94)对EMFAPP在EP中的阻燃性能进行了研究.EMFAPP在EP基体中阻燃性能优异,当其添加量大于7%时EP/EMFAPP均通过UL 94 V-0级,LOI值达27.0%以上.与未包裹APP相比,EMFAPP耐水性明显提高;经水处理(75℃,6天)后,EMFAPP/EP仍可保持良好的阻燃性能.采用热重分析对EMFAPP及其阻燃复合物的热降解行为进行了研究,EMFAPP能够促进成炭,EP/EMFAPP(8 wt%)在700℃残炭率达16.2%,但其低温稳定性有所下降.此外,利用热失重-红外联用对EMFAPP/EP的热降解行为进行了研究,探讨相关阻燃机理.     

The investigation of intumescent flame-retarded polypropylene using poly(hexamethylene terephthalamide) as carbonization agent

A novel intumescent flame retardant, containing ammonium polyphosphate (APP), and poly(hexamethylene terephthalamide) (PA6T), was prepared for flame retarding polypropylene (PP). The flame retardation of the PP composites was characterized by limiting oxygen index (LOI). The thermal degradation of the composites was investigated by means of thermogravimetric analysis (TG) and TG coupled with Fourier transform infrared spectroscopy (TG-FTIR). The morphology of the char obtained after combustion of the composites was studied by scanning electron microscopy. It has been found the intumescent flame retardant showed good flame retardancy, with the LOI value of the PA6T/APP/PP (5/25/70) system increasing from 17.5 to 32. Meanwhile, the TG and TG-FTIR work indicated that PA6T could be effective as a carbonization agent and there was a synergistic reaction between PA6T and APP, which effectively promoted the char formation of the PP composites. Moreover, it was revealed that uniform and compact intumescent char layer was formed after combustion of the intumescent flame retarded PP composites.     

Enhancement of a hyperbranched charring and foaming agent on flame retardancy of polyamide 6

A hyperbranched polyamine was prepared using an A₂ + B₃ approach. It acted as a hyperbranched charring and foaming agent (HCFA) in combination with ammonium polyphosphate (APP) to form a new intumescent flame retardant (IFR) system for polyamide 6 (PA6). Effect of HCFA on flame retardant and thermal degradation properties of IFR‐PA6 was investigated by limiting oxygen index (LOI), UL‐94 vertical burning, cone calorimeter, and thermogravimetric analysis (TGA) tests. The IFR system presented the most effective flame retardancy in PA6 when the weight ratio of APP to HCFA was 2:1. The LOI value of IFR‐PA6 could reach 36.5 with V‐0 rating when the IFR loading was 30 wt%. Even if the loading decreased to 25 wt%, IFR‐PA6 could still maintain V‐0 rating with an LOI value of 31. TGA curves indicated that APP would interact with both PA6 and HCFA in PA6/APP/HCFA composite under heating. The interaction between APP and HCFA improved the char formation ability of IFR system and then much more char was formed for PA6/APP/HCFA composite than for PA6/APP. Therefore, better flame retardancy was achieved. Moreover, the structure and morphology of char residue were studied by Fourier transform infrared (FTIR), X‐ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The results indicated that compact and foaming char layer containing P‐O‐C structure was formed for PA6/APP/HCFA system during combustion. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis of siloxane‐containing benzoxazine and its synergistic effect on flame retardancy of polyoxymethylene

A type of trialkoxysilane‐containing naphtholoxazine compound (Naph‐boz) was successfully synthesized and combined with ammonium polyphosphate/melamine (APP/ME) as an intumescent flame retardant (IFR) to improve the flame‐retardant efficiency of polyoxymethylene (POM). The Underwriters Laboratories 94 (UL94) vertical burning test, limiting oxygen index (LOI), cone calorimeter, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and Raman spectral analysis were used to study the flame‐retardant properties and related mechanism. The results showed that the formulation with 20 wt.% of APP, 6 wt.% of ME, and 4 wt.% of Naph‐boz passed UL94 V‐1 rating, and the LOI value was improved to 40.3%. Compared with pure POM, the IFR with Naph‐boz had greater reduction in peak heat release rate (lower 74.9%) and total heat release (lower 40.2%). SEM images showed that compact and reinforcing charred layer was formed during the POM/IFR/4Naph‐boz samples combustion, which was beneficial at reducing and maintaining low combustion parameters throughout the cone calorimeter test. The synergistic flame‐retardant effect between Naph‐boz and APP/ME was considered as the reason for the improvement in flame retardancy POM. Furthermore, because of the Naph‐boz was conducive to the compatibility between the flame retardants and matrix, the notched Izod impact strength of POM/IFR/4Naph‐boz composite was higher than that of POM/IFR system.     

Sol–gel treatments for enhancing flame retardancy and thermal stability of cotton fabrics: optimisation of the process and evaluation of the durability

Cotton fabrics have been treated by sol–gel processes in order to create a silica compact coating on the fibres to enhance their thermal stability and flame retardancy. The effect of process parameters such as silica precursor:water molar ratio and drying conditions (temperature and time) has been thoroughly investigated, aiming at optimization of target properties. Thermogravimetry and cone calorimetry have been respectively used to assess thermal stability and combustion behaviour of treated fabrics. Coating durability to different washing programmes has been evaluated as well.     

Flame retardancy mechanisms of poly(1,4‐butylene terephthalate) containing microencapsulated ammonium polyphosphate and melamine cyanurate

The flame retardancy mechanisms of poly(1,4‐butylene terephthalate) (PBT) containing microencapsulated ammonium polyphosphate (MAPP) and melamine cyanurate (MC) were investigated via pyrolysis analysis (thermogravimetric analysis (TGA), real‐time Fourier transform infrared (FTIR), TG‐IR), cone calorimeter test, combustion tests (limited oxygen index (LOI), UL‐94), and residue analysis (scanning electron microscopy (SEM)). A loading of 20 wt% MC to PBT gave the PBT composites an LOI of 26%, V‐2 classification in UL‐94 test and a high peak heat release rate (HRR) in cone calorimeter test. Adding APP to PBT/MC composites did not improve their flame retardancy. In comparison with the addition of ammonium polyphosphate (APP) to PBT, MAPP with silica gel shell and MAPP with polyurethane shell both promoted the intumescent char‐forming and improved the flame retardancy of PBT through different mechanisms in the presence of MC. These two halogen‐free PBT composites with V‐0 classification according to UL‐94 test were obtained; their LOI were 32 and 33%, respectively. Copyright © 2010 John Wiley & Sons, Ltd.     

Flame retardant properties and mechanism of an efficient intumescent flame retardant PLA composites

The charring agent (CNCA‐DA) containing triazine and benzene rings was combined with ammonium polyphosphate (APP) to form intumescent flame retardant (IFR), and it was occupied to modify polylactide (PLA). The flame retardant properties and mechanism of flame retardant PLA composites were investigated by the limited oxygen index (LOI), vertical burning test (UL‐94), thermogravimetric analysis, microscale combustion calorimetry, scanning electron microscopy, laser Raman spectroscopy analysis and X‐ray photoelectron spectroscopy. The analysis from LOI and UL‐94 presented that the IFR was very effective in flame retardancy of PLA. When the weight ratio of APP to CNCA‐DA was 3:1, and the IFR loading was 30%, the IFR showed the best effect, and the LOI value reached 45.6%. It was found that when 20 wt% IFR was loaded, the flame retardancy of PLA/IFR still passed UL‐94 V‐0 rating, and its LOI value reached 32.8%. The microscale combustion calorimetry results showed that PLA/IFR had lower heat release rate, total heat release, and heat release capacity than other composites, and there was an obvious synergistic effect between APP and CNCA‐DA for PLA. IFR containing APP/CNCA‐DA had good thermal stability and char‐forming ability with the char residue 29.3% at 800°C under N₂ atmosphere. Scanning electron microscopy observation further indicated that IFR could promote forming continuous and compact intumescent char layer. The laser Raman spectroscopy analysis and X‐ray photoelectron spectroscopy analysis results indicated that an appropriate graphitization degree of the residue char was formed, and more O and N were remained to form more cross‐linking structure. Copyright © 2016 John Wiley & Sons, Ltd.     

Fire retarded polyurethane foam composites based on steel slag/ammonium polyphosphate system: A novel strategy for utilization of metallurgical solid waste

A series of FR-RPUF composites were prepared by a one-step water foaming process with ammonium polyphosphate (APP) and steel slag (SS) as flame retardants. Thermogravimetric analysis (TG), limiting oxygen index (LOI), UL-94 vertical combustion test, microscale combustion calorimetry (MCC), TG-Fourier transform infrared spectrometry (TG-FTIR), scanning electron microscopy (SEM), Raman spectra and FTIR were used to investigate the thermal stability, flame retardancy, combustion performance, gas phase products, and char residue morphology of FR-RPUF composites. TG test results showed that the initial decomposition temperature (T_-5wt%) and char residue rate at 700°C of RPUF/APP/SS composites were significantly enhanced by the addition of APP and SS, and the thermal stability of the composites was improved. Flame retardant test results confirmed the significantly increased LOI values of RPUF/APP/SS composites with V-0 rating. TG-FTIR also confirmed the obviously decreased release of toxic gases and flammable gases in the combustion of RPUF/APP/SS composites. SEM and Raman spectra of char residues for the composites suggested that APP/SS system improved the compactness and graphitization degree of char layer for RPUF/APP/SS composite. The above researches provide a new strategy for the utilization of SS in fire safety engineering.     

Flame retardancy properties of α-zirconium phosphate based composites

α-Zr phosphate (hereafter referred to as ZrP) based composites were prepared by melt blending in order to improve the flame retardancy properties of polyamide 6 (PA6), polyethylene terephthalate (PET), polypropylene (PP) and ethylene vinyl acetate copolymer (EVA). Different morphologies are distinguishable by electron microscopy: PA6-ZrP seems to be a nanocomposite by Transmission Electron Microscopy (TEM) whereas PET-, PP- and EVA-ZrP blends appear micro-composites by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) analyses. ZrP acts as flame retardant in PA6 reducing the total heat evolved and consequently the heat release rate during the combustion measured by cone calorimetry. Moreover, ZrP reduces the flammability of PET and EVA acting in synergistic effect with phosphorous based flame retardants. Indeed, it is showed that it is possible to reduce the amount of phosphorous flame retardant adding ZrP to reach UL94 classification V0 for both polymers.     

Synthesis of a novel ionic liquid containing phosphorus and its application in intumescent flame retardant polypropylene system

A novel ionic liquid containing phosphorus ([PCMIM]Cl) was synthesized and characterized by FTIR, ¹H NMR, ¹³C NMR and ³¹P NMR. Moreover, a new intumescent flame retardant (IFR) system, which was composed of [PCMIM]Cl and ammonium polyphosphate (APP), was used to impart flame retardancy and dripping resistance to polypropylene (PP). The flammability and thermal behaviors of intumescent flame‐retarded PP (PP/IFR) composites were evaluated by limiting oxygen index (LOI), UL‐94 test, thermogravimetric analysis (TGA) and cone calorimeter test. It was found that there was an obvious synergistic effect between [PCMIM]Cl and APP. When the weight ratio of [PCMIM]Cl and APP was 1:5 and the total amount of IFR was kept at 30 wt%, LOI value of PP/IFR composite reached 31.8, and V‐0 rating was obtained. Moreover, both the peak heat release rate and the peak mass loss rate of PP/IFR composites decreased significantly relative to PP and PP/APP composite from cone calorimeter analysis. The TGA curves suggested that [PCMIM]Cl had good ability of char formation, and when combined with APP, it could greatly promote the char formation of PP/IFR composites, hence improved the flame retardancy. Additionally, the rheological behaviors and mechanical properties of PP/IFR composites were also investigated, and it was found that [PCMIM]Cl could also serve as an efficient lubricant and compatibilizer between APP and PP, endowing the materials with satisfying processability and mechanical properties. Copyright © 2013 John Wiley & Sons, Ltd.     

Great enhancement of efficiency of intumescent flame retardants by titanate coupling agent and polysiloxane

Modified intumescent flame retardants (MIFRs) and polysiloxane (APID) have been used in combination to enhance the flame retardancy of polypropylene (PP). The IFR system was composed of melamine (MEL), ammonium polyphosphate (APP) and pentaerythritol (PER). Aimed to improve the thermal stability of the IFR and its dispersivity in PP, titanate coupling agent NDZ‐201 was used to modify the IFRs via ball milling. MIFRs and APID have a cooperative effect on the flame retardant properties of PP. With 25 wt.% of MIFR and APID, the flame retardant sample (PPMA) was rated V0 for UL‐94, the LOI value was 34.3%, and the peak heat release rate (PHRR) was reduced by 80% in cone calorimeter test. In addition, APID could improve the compatibility of MIFR with the PP matrix, thereby increasing the mechanical properties of PP blends. The flame retardant effect of APID and MIFR in PP was presented in the condensed phase resulting in a rigid, thermally stable and expanded carbon layer due to different char structures.     

Efficiency of wollastonite and ammonium polyphosphate combinations on flame retardancy of polystyrene

The thermal and fire properties of polystyrene (PS) flame retarded by a system composed of ammonium polyphosphate (APP) and wollastonite (W) were investigated by thermogravimetric analysis, pyrolysis‐combustion flow calorimeter, pyrolysis gas chromatography mass spectrometry, cone calorimetry and epiradiator. The combustion residues were observed by scanning electron microscopy/energy dispersive X‐ray spectroscopy and analyzed by X‐ray diffraction. The combination of both additives enables increasing the thermal stability of PS while increasing simultaneously the high temperature residue. The peak of HRR was also significantly reduced while time to ignition varied depending on the composition. It was shown that the degradation pathway of PS was affected by the presence of the additives implying a reduction of the effective heat of combustion. In the condensed phase, APP decomposition promotes char formation and favors the reactivity between phosphorus and silicate. A layer composed of char, W and a mixture of calcium and silicon phosphate is formed at the sample surface during combustion. This layer is cohesive enough to limit the release of combustible gases to the gas phase. Moreover, the thermally stable protective layer reaches high temperature enabling the re‐irradiation of a part of the incident heat flux. The flame retardancy of PS is thus enhanced. Copyright © 2012 John Wiley & Sons, Ltd.     

Thermal and Mechanical Properties of Zeolite Filled Ethylene Vinyl Acetate Composites

Ethylene vinyl acetate (EVA) composites filled with zeolite (25 vol.%) were prepared using an internal mixer followed by compression molding machine. In order to enhance the thermal properties and fire retardancy of the composites, an intumescent flame retardant consisting of ammonium polyphosphate (APP)/pentaerythritol (PER) was incorporated into the composites. Two kinds of flame retardants were used which are untreated APP (APP1) and silane treated APP (APP2), where their effectiveness was evaluated by means of differential scanning calorimetry (DSC) and also thermogravimetric analysis (TGA). The results showed that both types of flame retardants have the ability to enhance the thermal stability of EVA/zeolite composites by producing charred layer which protects the underlying composites from the action of flame. Moreover, the incorporation of APP1 and APP2 has a significant effect on the composites degree of crystallinity. Meanwhile the results of tensile testing showed that the composites with APP2/PER exhibit better tensile properties compared to that with APP1/PER. This is expected since the application of silane-treated APP (APP2) could improve the dispersion of APP particles within EVA matrix.