Organophosphorus-hydrazides as potential reactive flame retardants for epoxy

2019 ◽  
Vol 38 (1) ◽  
pp. 28-52 ◽  
Author(s):  
Alexander B Morgan ◽  
Vladimir Benin ◽  
Donald A Klosterman ◽  
Abdulhamid Bin Sulayman ◽  
Mustafa Mukhtar ◽  
...  

For structural composites used in vehicles and aircraft, flame retardant chemistries which enhance char formation and reduce heat release are preferred. Phosphorus-based and phosphorus–nitrogen flame retardants for epoxies have been well studied to date, but phosphorus hydrazides have not been studied for their flame-retardant potential in epoxy. These hydrazides offer some novel structures and they can potentially offer a combination of vapor and condensed phase flame retardant action. A series of eight compounds were systematically investigated in this study as reactive flame retardants in a bisphenol F epoxy/aliphatic amine resin system at a level of 2.5 wt% phosphorus. Results suggest that the phosphorus hydrazides react with the epoxy during thermal decomposition, and they also release nitrogen during flaming combustion of the epoxy matrix. The observed reactions resulted in increased char yields and reduced total heat release, while simultaneously lowering heat of combustion and total smoke release.

2014 ◽  
Vol 881-883 ◽  
pp. 863-866
Author(s):  
Chao Peng ◽  
Shi Bin Nie ◽  
Lei Liu ◽  
Qi Lin He ◽  
Yuan Hu ◽  
...  

Nanoporous nickel phosphates (VSB-1) was synthesized by hydrothermal method. Then VSB-1 was added to the ammonium polyphosphate and pentaerythritol system in polypropylene (PP) matrix.The synergistic effect of VSB-1 with intumescent flame retardants (IFR) was studied by cone calorimetry test. The results of cone calorimetry show that heat release rate peak (pHRR) and total heat release (THR) of intumescent flame retardant PP with 2wt% VSB-1 decrease remarkably compared with that of without VSB-1. The pHRR and THR decrease respectively from 1140 to 286.0 kW/m2, and from 96.0 to 63.2 MJ/m2.


2013 ◽  
Vol 785-786 ◽  
pp. 131-137
Author(s):  
Ze Jiang Zhang ◽  
Li Jun Li ◽  
Feng Li ◽  
Jin He ◽  
Zi Qiong Gan

Influence of different flame retardants on the heat release performance of the rigid polyurethane foam (RPF) was studied in this paper. It was found that adding antimony trioxide (ATT) in RPF, heat release rate of RPF was slightly reduced, total heat release was significantly decreased but peak of heat release temperature was decreased. Therefore, ATT was not an excellent flame retardant for RPF. When adding ammonium polyphosphate (APP) in RPF, total heat release of RPF was significantly decreased, ignition temperature was significantly improved and heat release rate was not changed. Melamine polyphosphate (MPOP) could quickly reduce total heat release of RPF so its flame retardant effect was the best. Nitrogen-based flame retardants could reduce peak of heat release rate of RPF. APP, MPOP and nitrogen-based flame retardants were all better flame retardants for RPF. Small amount of magnesium hydroxide (MH) could increase total heat release of RPF.


2021 ◽  
pp. 096739112110245
Author(s):  
Jiangbo Wang

A novel phosphorus-silicon containing flame-retardant DOPO-V-PA was used to wrap carbon nanotubes (CNTs). The results of FTIR, XPS, TEM and TGA measurements exhibited that DOPO-V-PA has been successfully grafted onto the surfaces of CNTs, and the CNTs-DOPO-V-PA was obtained. The CNTs-DOPO-V-PA was subsequently incorporated into epoxy resin (EP) for improving the flame retardancy and dispersion. Compared with pure EP, the addition of 2 wt% CNTs-DOPO-V-PA into the EP matrix could achieve better flame retardancy of EP nanocomposites, such as a 30.5% reduction in peak heat release rate (PHRR) and 8.1% reduction in total heat release (THR). Furthermore, DMTA results clearly indicated that the dispersion for CNTs-DOPO-V-PA in EP matrix was better than pristine CNTs.


Materials ◽  
2020 ◽  
Vol 13 (5) ◽  
pp. 1251
Author(s):  
Yilin Liu ◽  
Bin Li ◽  
Miaojun Xu ◽  
Lili Wang

Ethylene vinyl acetate (EVA) copolymer has been used extensively in many fields. However, EVA is flammable and releases CO gas during burning. In this work, a composite flame retardant with ammonium polyphosphate (APP), a charring–foaming agent (CFA), and a layered double hydroxide (LDH) containing rare-earth elements (REEs) was obtained and used to improve the flame retardancy, thermal stability, and smoke suppression for an EVA matrix. The thermal analysis showed that the maximum thermal degradation temperature of all composites increased by more than 37 °C compared with that of pure EVA. S-LaMgAl/APP/CFA/EVA, S-CeMgAl/APP/CFA/EVA, and S-NdMgAl/APP/CFA/EVA could achieve self-extinguishing behavior according to the UL-94 tests (V-0 rating). The peak heat release rate (pk-HRR) indicated that all LDHs containing REEs obviously reduced the fire strength in comparison with S-MgAl. In particular, pk-HRR of S-LaMgAl/APP/CFA/EVA, S-CeMgAl/APP/CFA/EVA and S-NdMgAl/APP/CFA/EVA were all decreased by more than 82% in comparison with pure EVA. Furthermore, the total heat release (THR), smoke production rate (SPR), and production rate of CO (COP) also decreased significantly. The average mass loss rate (AMLR) confirmed that the flame retardant exerted an effect in the condensed phase of the composites. Meanwhile, the combination of APP, CFA, and LDH containing REEs allowed the EVA matrix to maintain good mechanical properties.


Polymers ◽  
2021 ◽  
Vol 13 (23) ◽  
pp. 4216
Author(s):  
Peixin Yang ◽  
Hanguang Wu ◽  
Feifei Yang ◽  
Jie Yang ◽  
Rui Wang ◽  
...  

In this study, a novel flame retardant (PMrG) was developed by self-assembling melamine and phytic acid (PA) onto rGO, and then applying it to the improvement of the flame resistance of PLA. PMrG simultaneously decreases the peak heat release rate (pHRR) and the total heat release (THR) of the composite during combustion, and enhances the LOI value and the time to ignition (TTI), thus significantly improving the flame retardancy of the composite. The flame retardant mechanism of the PMrG is also investigated. On one hand, the dehydration of PA and the decomposition of melamine in PMrG generate non-flammable volatiles, such as H2O and NH3, which dilute the oxygen concentration around the combustion front of the composite. On the other hand, the rGO, melamine, and PA components in PMrG create a synergistic effect in promoting the formation of a compact char layer during the combustion, which plays a barrier role and effectively suppresses the release of heat and smoke. In addition, the PMrGs in PLA exert a positive effect on the crystallization of the PLA matrix, thus playing the role of nucleation agent.


BioResources ◽  
2020 ◽  
Vol 16 (1) ◽  
pp. 1311-1324
Author(s):  
Yating Hua ◽  
Chungui Du ◽  
Huilong Yu ◽  
Ailian Hu ◽  
Rui Peng ◽  
...  

Flame-retardant silicate-intercalated calcium aluminum hydrotalcites (CaAl-SiO3-LDHs) were synthesized to treat bamboo for retardancy, to overcome the bamboo’s flammability and reduce the production of toxic smoke during combustion. The microstructure, elemental composition, flame retardancy, and smoke suppression characteristics of the bamboo before and after the fire-retardant treatment with different pressure impregnation were studied using a scanning electron microscope (SEM), elemental analysis (EDX), and cone calorimetry. It was found that CaAl-SiO3-LDHs flame retardants can effectively fill and cover the cell wall surface and the cell cavity of bamboo without damaging the microstructure. As compared to the non-flame-retardant bamboo, the heat release rate (HRR) of the CaAl-SiO3-LDHs flame-retardant bamboo was significantly reduced, the total heat release (THR) decreased by 31.3%, the residue mass increased by 51.4%, the time to ignition (TTI) delay rate reached 77.8%, the mass loss rate (MLR) decreased, and the carbon formation improved. Additionally, as compared to the non-flame-retardant bamboo, the total smoke release (TSR) of the CaAl-SiO3-LDHs flame-retardant bamboo decreased by 38.9%, and the carbon monoxide yield (YCO) approached zero. Thus, the CaAl-SiO3-LDHs flame-retardant bamboo has excellent flame-retardancy and smoke suppression characteristics.


Materials ◽  
2019 ◽  
Vol 13 (1) ◽  
pp. 158 ◽  
Author(s):  
Ru Zhou ◽  
Wenjuan Li ◽  
Jingjing Mu ◽  
Yanming Ding ◽  
Juncheng Jiang

A series of novel flame retardants (aluminum diethylphosphinate and melamine) were used to improve the fire performance of phenolic resin. Fourier transform infrared spectroscopy (FTIR) was used to characterize the modification results. Thermo-gravimetric analysis (TGA) was used to study the thermal decomposition of phenolic resin system, and the flame retardancy of phenolic resin system was tested by vertical combustion test (UL-94) and limiting oxygen index (LOI). The combustion properties of modified phenolic resin were further tested with a cone calorimeter(CCT). Finally, the structure of carbon residue layer was measured by scanning electron microscopy (SEM). The results show that with the introduction of 10 wt % aluminum diethylphosphinate in phenolic resin, the LOI reaches 33.1%, residual carbon content increase to 55%. The heat release rate (HRR) decreased to 245.6 kW/m2, and the total heat release (THR) decreased to 58.6 MJ/m2. By adding 10 wt % aluminum diethylphosphinate and 3 wt % melamine, the flame retardancy of the modified resin can pass UL-94 V-0 flame retardant grade, LOI reaches 34.6%, residual carbon content increase to 59.5%. The HRR decreases to 196.2 kW/m2 at 196 s, relatively pure phenolic resin decreased by 35.5%, and THR decreased to 51 MJ/m2. Compared with pure phenolic resin, the heat release rate and total heat release of modified phenolic resin decreased significantly. This suggests that aluminum diethylphosphinate and melamine play a nitrogen-phosphorus synergistic effect in the phenolic resin, which improves the thermal stability and flame retardancy of the phenolic resin.


2013 ◽  
Vol 438-439 ◽  
pp. 387-390 ◽  
Author(s):  
Da Liang Liu ◽  
Yi Zhong Yan ◽  
Yun Yong Huang ◽  
Jia Liang Yao ◽  
Jian Bo Yuan

Flame retardants modified asphalt with SBS flame retardant SMA hybrid material was prepared, flame retardant performances of SMA mixture was studied by the cone calorimeter. The results show that adding 12% flame retardant with SBS modified asphalt in preparation of flame retardant SMA mixture, the peak heat release rate values than the non-flame retardant asphalt mixture decreased by 4.02 kW/m2, and the heat release rate values were significantly reduced, the total heat and the amount of smoke of flame retardant asphalt mixture released less than the non-flame retardant asphalt mixture.


2015 ◽  
Vol 10 (3) ◽  
pp. 155892501501000 ◽  
Author(s):  
Xiaoli Yin ◽  
Mourad Krifa ◽  
Joseph H. Koo

Polyamide 6 (PA6) was melt-blended with an intumescent flame retardant (FR), multi-wall carbon nanotubes (MWNTs), and nanoclay particles to produce multi-component FR-PA6 nanocomposites. FR-PA6 nanofibers were processed from varied nanocomposite formulations via electrospinning. Electrospinnability, morphology, along with combustion and thermal properties of the nanofibers were investigated. Both the bulk-form nanocomposites and the electrospun nanofiber membranes exhibited significantly improved combustion properties, including both Heat Release Rate and Total Heat Release. On the other hand, thermal stability appeared compromised. With proper FR additive concentrations, synergism between MWNTs and nanoclay was observed.


Holzforschung ◽  
2020 ◽  
Vol 0 (0) ◽  
Author(s):  
Petri Widsten ◽  
Tarja Tamminen ◽  
Antti Paajanen ◽  
Tuula Hakkarainen ◽  
Tiina Liitiä

AbstractPolyolefins used in building materials and furniture require the use of flame-retardant (FR) additives to improve their fire safety. Such additives should be safe to humans and the environment, and preferably bio-based. In the present work, the FR performance of unmodified and chemically modified technical lignins was compared to that of the ammonium polyphosphate/pentaerythritol (APP/PER) intumescent system in a polypropylene (PP) matrix. Micro-scale combustion calorimetry (MCC) was used to study the peak heat release rate (PHR), temperature at PHR (TPHR), total heat release (THR) and char yield upon thermal decomposition of milligram-scale specimens. The PP/lignin composites showed up to 41% lower PHR and up to 36% lower THR compared to pure PP as well as large char residues. Based on the same parameters, especially the PP/lignin composites made with modified lignins outperformed the reference PP/APP/PER system and the PP/APP/lignin composites where unmodified lignin was used with APP. The most promising PP/lignin composites were prepared with partially demethylated/demethoxylated and depolymerised kraft lignin (‘CatLignin’), modified by the Mannich reaction to a nitrogen content of 13.5%.


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