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1.
DOPO and boron nitride (BN) fillers with different particle sizes and several loadings were employed to improve the properties of cyanate ester (CE) resin. The effects of BN content and particle size on the thermal conductivity of the BN‐DOPO/CE ternary composites were discussed. The influence of enhancing the thermal conductivity of the ternary composites on their flame retardancy was studied. The consequences showed that increasing the thermal conductivity of BN‐DOPO/CE composites had an active impact on their flame retardancy. Approving flame retardancy of the ternary composites was certified by the high limiting oxygen index (LOI), UL‐94 rating of V‐0, and low heat release rate (HRR) and total heat release (THR). For instance, in contrast with pure CE matrix, peak of HRR (pk‐HRR), average of HRR (av‐HRR), THR, and average of effective heat of combustion (av‐EHC) of CEP/BN0.5 μm/10 composite were decreased by 51.7%, 33.8%, 18.7%, and 18.9%, respectively. Thermal gravimetry analysis (TGA) showed that the addition of BN fillers improves the thermal stability of the composites. Moreover, the ternary composites possess good dielectric properties. Their dielectric constants (ε) are less than 3, and dielectric loss tangent (tgδ) values are lower than neat CE resin.  相似文献   

2.
A novel activated carbon spheres (ACS)@SnO2@NiO hierarchical hybrid architecture was first synthesized and applied for enhancing the flame retardancy of epoxy (EP) resin via a cooperative effect. Herein, using activated carbon microspheres as the template, SnO2 and NiO nanospheres were successively anchored to it by a sedimentation‐calcination strategy. The well‐designed ACS@SnO2@NiO significantly enhanced the flame retardancy for consistency of EP composites, as demonstrated by thermogravimetric and cone calorimeter experiments. For instance, the incorporation of 2 wt% ACS@SnO2@NiO decreased by 15.5% maximum in the total smoke production, accompanying the higher graphitized char layer. In addition, the synergetic mechanism of flame retardancy between ACS@SnO2@NiO and aluminum hypophosphite (AHP) was investigated. The obtained sample satisfied the UL‐94 V‐0 rating with a 5.0 wt% addition of AHP and ACS@SnO2@NiO (the ratio of the mass fraction of AHP to ACS@SnO2@NiO is 4.5:0.5). Notably, the incorporation of AHP and ACS@SnO2@NiO resulted in a significant decrease in the fire hazard properties of EP resin; for instance, 4.5AHP‐0.5ACS@SnO2@NiO/EP resulted in a maximum decrease of 32.4% in the total smoke production as compared with that of pure EP resin. It should be noted that the improved flame‐retardant performance for the EP composites is primarily attributed to the synergistic effect of ACS@SnO2@NiO and AHP in promoting the formation of residual char in the condensed phase.  相似文献   

3.
Flame retardants from vanillin when utilized together with ammonium polyphosphate (APP) yield excellent synergistic flame retardancy toward epoxy resins. Bisphenol A epoxy resins have been widely used due to their excellent mechanical properties, chemical resistance, electrical properties, adhesion, etc., while they are flammable. Environment‐friendly and bio‐based flame retardants have captured increasing attention due to their ecological necessity. In this paper, 3 bio‐based flame retardants were synthesized from abundant and more importantly renewable vanillin, and their chemical structures were determined by 1H NMR and 13C NMR. They were used together with APP (an environment‐friendly commercial flame retardant) to improve the fire resistance of bisphenol A epoxy resin. With the addition APP content of 15 phr, the modified bisphenol A epoxy resin could reach UL‐94V0 rating during vertical burning test and limit oxygen index values of above 35%, but reducing APP content to 10 phr, the flame retardancy became very poor. With the total addition content of 10 phr, the epoxy resins modified by 7 to 9 phr APP and 1 to 3 phr bio‐based flame retardants with epoxy groups or more benzene rings showed excellent flame retardancy with UL‐94V0 rating and limit oxygen index values of around 29%. The Tgs of the epoxy resins could be remained or even increased after introducing bio‐based flame retardants, as the control; those of APP alone‐modified epoxy resins compromised a lot. The green synergistic flame‐retardant systems have a great potential to be used in high‐performance materials.  相似文献   

4.
Molybdenum trioxide (MoO3) microrods, nanofibers, and nanoplates were synthesized via the hydrothermal method and high‐temperature calcination method, respectively. Then the MoO3 was added into polyurethane elastomer, respectively. The flame retardancy and smoke suppression of the composites added with different MoO3 were studied by thermal gravimetric analysis, cone calorimeter, and smoke density. The results show that the three kinds of MoO3 with different morphologies could promote the formation of char and possess flame retardancy and smoke suppression, and MoO3 nanofibers exhibit a higher degree of flame retardancy, and 1 wt% addition could make the peak heat release rate of polyurethane elastomer composites reduce from 881.6 kW m?2 for a pure sample to 343.4 kW m?2, a decrease by 61.0%. As for smoke suppression, MoO3 nanoplates possess the best smoke suppression; 5 wt% could decrease a pure sample's smoke density by 41.3% from 361 to 212. Moreover, the char residue of composites after combustion was analyzed by Raman spectra and X‐ray photoelectron spectroscopy, and the flame retardancy and smoke suppression mechanisms of MoO3 were discussed.  相似文献   

5.
A novel mono‐component intumescent flame retardant named pentaerythritol phosphate melamine salt (PPMS)‐hybrid bismuth oxide (PPMS‐Bi2O3) was synthesized and carefully characterized by FTIR, 1H NMR, 31P NMR, SEM‐EDS, and TG analyses. Then, PPMS‐Bi2O3 was utilized as flame retardant for epoxy resins (EPs), and the thermal stability, flame retardancy, and smoke suppression properties of EP composites were investigated. TG results show that PPMS‐Bi2O3 is more conducive to enhance the thermal stability and char forming ability of EP composites compared with the same addition of PPMS or the mixture of PPMS and Bi2O3, and this positive effect is enhanced with the increasing Bi2O3 content. Cone calorimeter test reveals that the PPMS‐Bi2O3 can effectively reduce the heat release and smoke production in comparison with PPMS or the mixture of PPMS and Bi2O3 due to the formation of a more compact and intumescent char against fire, as judged by digital photographs and SEM images. EDS analysis indicates that the combination PPMS and Bi2O3 by hydrogen bonds promotes to generate more phosphorus‐rich and aromatization structures in the condensed phase that enhance the barrier effect and anti‐oxidation ability of the char, thus imparting higher flame retardant and smoke suppression efficiencies to EP composites.  相似文献   

6.
《先进技术聚合物》2018,29(4):1242-1254
Extensive application of epoxy resins (EPs) is highly limited by their intrinsic flammability. Combining EPs with nanoparticles and phosphorus‐nitrogen flame retardants is an effective approach to overcome the drawback. In this work, simultaneous incorporation of octa‐aminophenyl polyhedral oligomeric silsesquioxanes (OapPOSS) and polyphosphazene into EP was reported for the first time. Significantly, reduced peak of heat release rate and UL‐94 V‐0 rating were achieved by tuning suitable ratios of polyphosphazene and OapPOSS for EP composites. During combustion, polyphosphazene promoted char formation and released nonflammable gases such as CO2, NH3, and N2 to dilute oxygen concentration and cool pyrolysis zone. Moreover, numerous phosphorus‐containing species acting as free radical scavengers were generated during degradation. Silicon dioxide evolving from OapPOSS protected char residues from thermal degradation. This study provides a novel method to fabricate high‐performance flame‐retardant EP composites, which have potential applications in the field of electrics and electronics.  相似文献   

7.
Mechanical properties of advanced composites are often impaired by flame retardants. The least adverse effect is found with synergistic combination of antimony oxides and brominated epoxies. Where low smoke generation is absolutely necessary phenolic resins are used. The new development of combining epoxy and phenolic resin layers in structural applications with high flame retardancy is introduced.  相似文献   

8.
The effects of lanthanum oxide (La2O3) as a synergistic agent on the flame retardancy of intumescent flame retardant polypropylene composites (IFR-PP) were studied, and the new IFR system mainly consisted of the charring-foaming agent (CFA) and ammonium polyphosphate (APP). The limiting oxygen index (LOI), UL-94 test, thermogravimetric analysis (TGA), cone calorimeter (CONE) and scanning electron microscopy (SEM) were used to evaluate the synergistic effects of La2O3. It was found that when IFR was fixed at 20 wt% in IFR-PP composites, only a little amount of La2O3 could enhance LOI value and pass the UL-94 V0 rating test (1.6 mm). The TGA data showed that La2O3 could enhance the thermal stability of the IFR-PP systems at high temperature and effectively increase the char residue formation. The CONE results revealed that La2O3 and IFR could clearly change the decomposition behavior of PP and form a char layer on the surface of the composites, consequently resulting in efficient reduction of the flammability parameters, such as heat release rate (HRR), total heat release (THR), smoke production rate (SPR), total smoke production (TSP), ignition time (IT) and so on. The morphological structures observed by SEM demonstrated that La2O3 could promote to form the homogenous and compact intumescent char layer. Thus, a suitable amount of La2O3 plays a synergistic effect in the flame retardancy and smoke suppression of IFR composites.  相似文献   

9.
《先进技术聚合物》2018,29(1):497-506
A novel phosphorus‐containing, nitrogen‐containing, and sulfur‐containing reactive flame retardant (BPD) was successfully synthesized by 1‐pot reaction. The intrinsic flame‐retardant epoxy resins were prepared by blending different content of BPD with diglycidyl ether of bisphenol‐A (DGEBA). Thermal stability, flame‐retardant properties, and combustion behaviors of EP/BPD thermosets were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), limited oxygen index (LOI) measurement, UL94 vertical burning test, and cone calorimeter test. The flame‐retardant mechanism of BPD was studied by TGA/infrared spectrometry (TGA‐FTIR), pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS), morphology, and chemical component analysis of the char residues. The results demonstrated that EP/BPD thermosets not only exhibited outstanding flame retardancy but also kept high glass transition temperature. EP/BPD‐1.0 thermoset achieved LOI value of 39.1% and UL94 V‐0 rating. In comparison to pure epoxy thermoset, the average of heat release rate (av‐HRR), total heat release (THR), and total smoke release (TSR) of EP/BPD‐1.0 thermoset were decreased by 35.8%, 36.5% and 16.5%, respectively. Although the phosphorus content of EP/BPD‐0.75 thermoset was lower than that of EP/DOPO thermoset, EP/BPD‐0.75 thermoset exhibited better flame retardancy than EP/DOPO thermoset. The significant improvement of flame retardancy of EP/BPD thermosets was ascribed to the blocking effect of phosphorus‐rich intumescent char in condensed phase, and the quenching and diluting effects of abundant phosphorus‐containing free radicals and nitrogen/sulfur‐containing inert gases in gaseous phase. There was flame‐retardant synergism between phosphorus, nitrogen, and sulfur of BPD.  相似文献   

10.
《先进技术聚合物》2018,29(1):641-648
To explore the component synergistic effect of boron/phosphorus compounds in epoxy resin (EP), 3 typical boron compounds, zinc borate (ZB), boron phosphate (BPO4), and boron oxide (B2O3), blended with phosphaphenanthrene compound TAD were incorporated into EP, respectively. All 3 boron/phosphorus compound systems inhibited heat release and increased residue yields and exerted smoke suppression effect. Among 3 boron/phosphorus compound systems, B2O3/TAD system brought best flame‐retardant effect to epoxy thermosets in improving the UL94 classification of EP composites and also reducing heat release most efficiently during combustion. B2O3 can interact with epoxy matrix and enhance the charring quantity and quality, resulting in obvious condensed‐phase flame‐retardant effect. The combination of condensed‐phase flame‐retardant effect from B2O3 and the gaseous‐phase flame‐retardant effect from TAD effectively optimized the action distribution between gaseous and condensed phases. Therefore, B2O3/TAD system generated component synergistic flame‐retardant effect in epoxy thermosets.  相似文献   

11.
As‐received sepiolite/epoxy systems and Fe3O4‐doped sepiolite/epoxy systems were prepared, and the contents of sepiolite and Fe3O4‐doped sepiolite were kept as 2 and 4 wt%, respectively. Compared with sepiolite, the effect of Fe3O4‐doped sepiolite on the flame retardancy, combustion properties, thermal degradation, thermal degradation kinetics and thermomechanical properties of epoxy resin was investigated systematically by limiting oxygen index (LOI), cone calorimeter (Cone), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). Some interesting results had been acquired. The addition of sepiolite decreased heat release rate, total smoke production and smoke production rate, and obviously improved LOI values of epoxy composites. Compared with sepiolite, the addition of Fe3O4‐doped sepiolite further reduced parameters mentioned above of epoxy composites, and further enhanced LOI values and char residues after cone test. There might be a synergistic effect between sepiolite and Fe3O4 on flame retardant epoxy composite. TGA results indicated that the addition of sepiolite had a slight effect on the thermal degradation of epoxy composites; however, the addition of Fe3O4‐doped sepiolite accelerated the thermal degradation of epoxy composites. DMA results showed that the addition of both sepiolite and Fe3O4‐doped sepiolite increased the glass transition temperature (Tg) of epoxy composite. The results obtained in this paper supplied an effective solution for developing excellent flame retardant properties of polymeric materials. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

12.
Epoxy resins modified by an organosoluble phosphorus‐containing bismaleimide (3,3′‐bis(maleimidophenyl) ­phenylphosphine oxide; BMPPPO) were prepared by simultaneously curing epoxy/diaminodiphenylmethane (DDM), and BMPPPO. The resulted epoxy resins were found to exhibit glass transition temperatures as high as 212 °C, thermal stability at temperatures over 350 °C, and excellent flame retardancy with Limited oxygen index (LOI) values around 40. Incorporation of BMPPPO into epoxy resins via the thermosetting blend was demonstrated to be an effective way to enhance the thermal properties and flame retardancy simultaneously. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

13.
A novel phosphorus‐containing silicone flame retardant (PDPSI) was prepared by Mannish reaction, and a series of PDPSI/PET composites were prepared by melt blending method. The nuclear magnetic resonance (1H NMR), Fourier transformation infrared (FTIR), and the thermogravimetric analyzer (TGA) results indicated that PDPSI showed network structure and owned good thermal stability, with the char residue of 62.2% at 800°C. The flame retardancy of PDPSI/PET composites was characterized by limiting oxygen index (LOI), vertical burning tests (UL‐94), and cone calorimeter (CCT). The results revealed that the addition amount of PDPSI was 5%, the LOI value of PDPSI/PET composites increased to 27.3%, and UL‐94 test passed V‐0 rating. When the PDPSI loading was 3%, PET composites showed excellent flame retardancy and smoke suppression, with a decrease in the peak heat release rate (PHRR) by 71.19% and the total smoke release (TSP) reduced from 14.4 to 11.1m2. The scanning electron microscopy (SEM) and FTIR results of char residue demonstrated that the flame‐retardant mechanism of PDPSI was solid phase flame retardant. PDPSI catalyzed the aromatization reaction of PET to promote the formation of a dense and continuous carbon layer, finally improving the flame retardancy and smoke suppression properties of PET.  相似文献   

14.
《先进技术聚合物》2018,29(4):1194-1205
Epoxy resin (EP) is more and more important in many fields, but its application is limited due to the inflammability in air of EP. Therefore, reducing the fire hazard of EP is necessary. In this work, a kind of hybrid flame retardant (α‐ZrP‐RGO) consisting of a 2‐dimensional inorganic reduced graphene oxide (RGO) modified with a planar‐like α‐zirconium phosphate (α‐ZrP) particles was prepared successfully via 1‐step hydrothermal method. The effects of α‐ZrP‐RGO on the thermal performance, flame retardancy, and smoke suppression of EP were investigated by preparing EP composites containing both EP and α‐ZrP‐RGO. Thermogravimetric results revealed that α‐ZrP‐RGO could improve the char yield of EP at 700°C obviously. In addition, compared with pure EP, the peak heat release rate and the total heat release of EP composites were decreased significantly, while the limited oxygen index of EP composites was increased. Meanwhile, the smoke production rate of EP composites was reduced obviously with the addition of α‐ZrP‐RGO. The enhanced flame retardancy and smoke suppression of EP composites were mainly attributed to not only the physical barrier effect of both α‐ZrP and RGO but also the catalytic effect of α‐ZrP during the combustion process of EP composites.  相似文献   

15.
A series of CeO2‐loaded titania nanotubes (CeO2‐TNTs) hybrid materials with different CeO2 loadings were synthesized by co‐precipitation method and then incorporated into epoxy resin (EP) to prepare CeO2‐TNTs flame‐retardant epoxy nanocomposites. Structure and morphology characterization indicated the successful synthesis of CeO2‐TNTs. The effect of CeO2‐TNTs with different CeO2 loading capacity on the flame retardance of EP was compared and analyzed by the thermogravimetric analysis, Cone and Raman. The results showed that CeO2 loading could increase the carbon residue of nanocomposites, reduce the peak heat release rate (PHRR) and total heat release (THR), and improve the fire safety of EP. The residual carbon content of EP/0.1CeO2‐TNTs sample at 700°C reached 19.8% with the lowest degradation rate, and the PHRR and THR were reduced to 680 kW/m2 and 32.9 MJ/m2, respectively. Such a significant improvement in flame‐retardant properties for EP could be attributed to the protective effect of CeO2‐TNTs.  相似文献   

16.
In this work, a DOPO‐based imidazolone derivative named DHI was synthesized using DOPO, 5‐amino‐2‐benzimidazolinone and 4‐hydroxybenzaldehyde as raw materials. The chemical structure of DHI was characterized by 1H‐NMR, 31P‐NMR and Fourier transform infrared spectra (FTIR). Then, a series of different flame‐retardant epoxy resin (EP) thermosets were prepared by mixing flame retardant DHI. The thermal properties of the cured EPs was investigated by thermogravimetry analysis (TGA) and differential scanning calorimeter (DSC), and the results showed the thermal stability and glass transition temperature (Tg) of the cured EP modified with DHI declined slightly compared with that of neat EP. The limited oxygen index (LOI) and UL94 test results exhibited DHI imparted good flame retardancy to EP. The EP‐4 (phosphorus content of 1.25%) possessed a LOI value of 36.5% and achieved a V‐0 rating. Furthermore, the peak of heat release rate (PHRR) and total heat release rate (THR) of EP‐4 decreased by 38.7% and 24.5%, respectively. Excitedly, the total smoke production (TSP) of EP‐4 sample declined by 62.5%, which meant DHI also made EP obtain excellent smoke suppression property. Moreover, the flame‐retardant mechanism was studied by scanning electron microscopy (SEM) and pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS). It was reasonable inferred that DHI could not only promote EP to form dense char layer in condensed phase, but also restrain combustion in gaseous phase through catching the free radicals sourced from the degradation of EP.  相似文献   

17.
《先进技术聚合物》2018,29(9):2505-2514
A novel catalyst consisting of SnO2 supported by activated carbon spheres (ACS), referred to as “ACS@SnO2,” was demonstrated as being much more efficient than either ACS or SnO2 alone. As such, it is capable of improving the thermal stability and flame retardancy of flexible poly (vinyl chloride) (fPVC). The resulting ACS@SnO2 composite exhibits a higher reactivity and excellent stability due to the presence of evenly dispersed SnO2 particles attached to the ACS, as well as the high degree of graphitization of the ACS. Smoke suppression and the synergistic flame‐retardant effect of the ACS@SnO2 on the fPVC were thoroughly investigated by performing a cone calorimeter test and thermogravimetric analysis. The cone calorimeter test data reveal that the addition of the ACS@SnO2 greatly improved the flame retardancy of the fPVC, with 32% and 58.4% decreases in the peak heat release rate and smoke production rate, respectively. This is attributed to the formation of a continuous and compact protective layer and the synergistic effects of the ACS and SnO2 in promoting the ability of the fPVC to isolate heat and oxygen. Furthermore, the ACS@SnO2/fPVC composite produced greatly increased amounts of char residue, thereby attenuating the fire hazard presented by fPVC composites.  相似文献   

18.
The flame retardancy of a novel intumescent flame‐retardant polypropylene (IFR‐PP) system, which was composed of a charring agent (CA), ammonium polyphosphate (APP), and polypropylene (PP), could be enhanced significantly by adding a small amount (1.0 wt%) of an organic montmorillonite (O‐MMT). The synergistic flame‐retardant effect was studied systematically. The thermal stability and combustion behavior of the flame‐retarded PP were also investigated by thermogravimetric analysis (TGA), limiting oxygen index (LOI), vertical burning test (UL‐94), scanning electronic microscopy (SEM), and cone calorimeter test (CCT). TGA results demonstrated that the onset decomposition temperatures of IFR‐PP samples, with or without O‐MMT, were higher than that of neat PP. Compared with IFR‐PP, the LOI value of IFR‐PP containing 1.0 wt% O‐MMT was increased from 30.8 to 33.0, and the UL‐94 rating was also enhanced to V‐0 from V‐1 when the total loading of flame retardant was the same. The cone calorimeter results showed that the IFR‐PP with 1.0 wt% of O‐MMT had the lowest heat release rate (HRR), total heat release (THR), total smoke production (TSP), CO production (COP), CO2 production (CO2P), and mass loss (ML) of all the studied IFR‐PP samples, with or without O‐MMT. All these results indicated that O‐MMT had a significantly synergistic effect on the flame‐retardancy of IFR‐PP at a low content of O‐MMT. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

19.
The flame‐retardant microcapsules were successfully fabricated with an aluminum hypophosphite (AHP) core. Fourier transform infrared (FTIR) and X‐ray photoelectron spectroscopy (XPS) were used to verify that AHP was encapsulated in the microcapsules, and thermogravimetry analysis showed that microencapsulated AHP (MAHP) possessed higher thermal stability than that of AHP. Then, a flame‐retardant and smoke suppression system for silicone foams (SiFs) was obtained through a synergistic effect of MAHP and zinc borate (2ZnO·3B2O3·3.5H2O). The mechanical properties, flame retardance, and smoke suppression of SiFs with MAHP and zinc borate were tested using the tensile test, limiting oxygen index (LOI) test, UL‐94 test, and cone calorimeter test. The mechanical properties indicated that the tensile strength and elongation at break of SiFs could evidently improve with the incorporation of MAHP. Compared with pure SiF, SiF8 with 4.5‐wt% MAHP and 1.5‐wt% zinc borate could achieve an LOI value of 30.7 vol% and an UL‐94 V‐0 rating, the time to ignition amplified almost six times, the peak heat release rate and total heat release were 51.10% and 46.00% less than that of pure SiF, respectively, the fire performance index increased nearly 13 times, and the fire growth index value was only 13.18% of pure SiF. Moreover, the partial substitution of zinc borate imparted a substantial improvement in both flame retardancy and smoke suppression. Especially, the peak smoke production rate and total smoke production of SiF8 were merely 38.46% and 38.84% of pure SiF.  相似文献   

20.
Poly(vinyl alcohol)/melamine phosphate composites (PVA/MP) as a novel halogen‐free, flame‐retardant foam matrix were prepared through thermal processing, and then their thermal stability and flame retardancy were investigated by thermo‐gravimetric analysis, micro‐scale combustion calorimeter, cone calorimeter, vertical burning test, and limiting oxygen index (LOI) test. It was found that the thermal stability and combustion properties of the PVA/MP composites could be influenced by the addition of MP. Compared with the control PVA sample (B‐PVA), in the PVA/MP (75/25) composites, the temperature at 5% mass loss (T5%) decreased about 10°C, the residual chars at 600°C increased by nearly 27%, the temperature at the maximum peak heat release rate (TP) shifted from 292°C to 452°C, and the total heat released and the heat release capacity (HRC) decreased by 28% and 14%, respectively. Moreover, the PVA/MP composites could reach LOI value up to 35% and UL94 classification V‐0, showing good flame retardancy. At the same time, both Fourier transform infrared and X‐ray photoelectron spectroscopy spectra of the residual chars from the PVA/MP composites demonstrated that the catalytic effect of MP on the dehydration and decarboxylation reactions of PVA, and the chemical reactivity of MP during the chars‐forming reactions could be used to account for the changed thermal stability and flame retardancy of the PVA/MP composites. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

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