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1.
《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   

2.
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   

3.
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   

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 curing and flame‐retardant agent (PEPA‐TMAC) was successfully synthesized. The chemical structure was characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). Use of PEPA‐TMAC as part of the curing agent in combination with another anhydride for a commercial epoxy resin (EP) was studied. Results of differential scanning calorimetry (DSC) indicated that PEPA‐TMAC was an effective curing agent for EP. The dynamic mechanical analysis (DMA) results showed that the glass transition temperature (Tg) and cross‐linking density (Ve) of EP composites exhibited an increase trend with the addition of PEPA‐TMAC. The limiting oxygen index (LOI) value of EP composites reached 26.9%, and the cone calorimeter results indicated that peak heat release rate (PHRR), total heat release (THR), smoke produce rate (SPR), and total smoke produce (TSP) remarkably decreased with increasing PEPA‐TMAC content. TGA data showed that the addition of PEPA‐TMAC greatly increased the amount of residual char during combustion. The morphology of the residual char was studied by SEM and showed that the addition of PEPA‐TMAC greatly increased the stability of EP composites. The thermogravimetric analysis (TGA), energy‐dispersive X‐ray spectroscopy (EDS), and FTIR results revealed the flame‐retardant mechanism that PEPA‐TMAC can promote the formation of charred layers with the phospho‐carbonaceous complexes in the condensed phase during burning of EP composites.  相似文献   

6.
Graphene‐polyaniline/nickel hydroxide ternary hybrid (RGO‐PANI/Ni(OH)2) was synthesized and incorporated into epoxy resin (EP) to improve the fire retardant property. Thermogravimetric analysis results showed that the RGO‐PANI/Ni(OH)2 nanohybrid could catalyze the thermal degradation of epoxy matrix that was essential to trigger the char formation. The char yield of the RGO‐PANI/Ni(OH)2/EP composite was improved compared with that of the samples with graphene and polyaniline only. With 3.0‐wt% RGO‐PANI/Ni(OH)2, significant reduction in peak heat release rate (40%) and peak smoke production rate (36%) was observed in the cone calorimeter tests. Thermogravimetric analysis/infrared spectrometry (TG‐IR) results indicated that the flammable volatiles of the RGO‐PANI/Ni(OH)2/EP composite was reduced compared with those of the EP and RGO‐PANI/EP. The superior flame retardant and smoke suppressant behaviors of the RGO‐PANI/Ni(OH)2 nanohybrid over RGO‐PANI were attributed to the combination of good barrier effect of graphene with catalytic ability of char formation of PANI and metal hydroxide.  相似文献   

7.
Reducing the fire hazard of polypropylene (PP) is an important research direction in the fields of fire safety materials. In this article, a novel Ni‐containing char‐forming agent (TTPN) was successfully synthesized, using tris(2‐hydroxyethyl) isocyanurate (THEIC), terephthalic acid, and nickel dihydrogen phosphate. Then, TTPN was combined with the silica‐gel microencapsulated ammonium polyphosphate (OS‐MCAPP) to prepare intumescent flame retardant PP composites. From the results of the limiting oxygen index (LOI) test and cone calorimeter, the composite containing 30% IFR (OS‐MCAPP: TTPN = 3:2) shows the highest LOI value of 33.5%, and its peak heat release rate is 275.5 kWm?2, decreased by 79.0% and 37.4% than those of pure PP and the composite containing the char‐forming agent without Ni. Meanwhile, the composite containing TTPN present the best smoke and CO2/CO suppression. The results indicate that TTPN has an excellent ability to dramatically reduce the fire hazard of PP.  相似文献   

8.
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   

9.
In this work, 12‐tungestocobaltic acid based organic–inorganic hybrid material, [Bmim]6CoW12O40 (CoW) was synthesized and applied as a synergist in polypropylene (PP)/intumescent flame retardant (IFR) composites. The flame retardant properties were investigated by the limiting oxygen index (LOI), UL‐94 vertical burning test, thermal gravimetric analyzer (TGA), cone calorimeter and scanning electron microscopy (SEM) etc. The results showed that the PP composites with 16 wt% IFR and 1 wt% CoW achieves the UL‐94 V‐0 rating and gets a LOI value 28.0. However, only add no less than 25 wt% single IFR, can the PP composites obtain the UL‐94 V‐0 rating, which suggests that CoW has good synergistic effects on flame retardancy of PP/IFR composites. In addition, the SEM and cone calorimeter tests indicated the CoW improves the quality of char layer. The rate of char formation has been enhanced also because of the existence of CoW. It is the combination of a better char quality and a high rate of char formation promoted by CoW that results in the excellent flame retardancy of PP/IFR composites. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

10.
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   

11.
《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   

12.
Kaolin clay was introduced into an intumescent flame retardant (IFR) system containing ammonium polyphosphate as an acid source and pentaerythritol as a carbonization agent in order to improve the thermal stability and flame retardancy of polypropylene (PP) composite. The flame retardancy and smoke suppression was evaluated by the limiting oxygen index, vertical burning UL‐94, and cone calorimeter (CONE) tests. The limiting oxygen index value was increased from 30 to 33 at the presence of 2 phr kaolin. The peak heat release rate value decreased from 1002 kW/m2 of neat PP to 318 kW/m2 of PP/40 phr IFR and then to 222 kW/m2 of PP/38 phr IFR/2 phr kaolin. The time of the peak heat release rate was significantly prolonged after the introduction of kaolin. The morphology of char after combustion was characterized by a scanning electron microscope, and it revealed more compact char structure that was obtained at the presence of kaolin. The mechanism of kaolin on improving the retardancy and smoke suppression of PP/IFR composite was proposed on the basis of X‐ray photoelectron spectroscopy analysis. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

13.
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.  相似文献   

14.
A kind of polyhedral oligomeric silsesquioxanes (POSS) containing the propoxyl‐epoxy and phenyl groups (pr‐ep‐Ph‐POSS) was synthesized via hydrolytic condensation reaction. Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry identified the structure of the pr‐ep‐Ph‐POSS, including major caged Si6O9 (T6), Si10O15 (T10), Si12O18 (T12), etc. The pr‐ep‐Ph‐POSS was applied into the epoxy resin to achieve EP/pr‐ep‐Ph‐POSS composites. Thermogravimetric analysis indicated that EP/pr‐ep‐Ph‐POSS showed excellent thermal properties than pure EP. The fire behaviors of EP/pr‐ep‐Ph‐POSS composites were evaluated based on the cone calorimetry, limiting oxygen index (LOI), UL‐94 vertical burning test, and smoke density test. The smoke density decreased by ~30%, the LOI value reached to 26.4%, dripping was inhibited, and the peak of heat release rate decreased by ~62%. X‐ray photoelectron spectroscopy analysis and FTIR indicated that protective‐barrier effect is the main flame‐retardant mode of action for pr‐ep‐Ph‐POSS, due to the formation of the Si‐O‐Si, Si‐O‐C, and Si‐C condensed phase, which improve the thermal stability, strength, and integrity of the char layer.  相似文献   

15.
Novel intumescent flame retardant polypropylene (PP) composites were prepared based on a char forming agent (CFA) and silica-gel microencapsulated ammonium polyphosphate (Si-MCAPP). The thermal and flame retardancy of flame retardant PP composites were investigated by limiting oxygen index, UL-94 test, cone calorimetry, thermogravimetric analysis, scanning electron micrograph, and water resistance test. The results of cone calorimetry show that the flame retardant properties of PP with 30 wt% novel intumescent flame retardants (CFA/Si-MCAPP = 1:3) improve greatly. The peak heat release rate and total heat release decrease, respectively, from 1,140.0 to 156.8 kW m?2 and from 96.0 to 29.5 MJ m?2. The PP composite with CFA/Si-MCAPP = 1:3 has the excellent water resistance, and it can still obtain a UL-94 V-0 rating after 168 h soaking in water.  相似文献   

16.
《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   

17.
In this work, kaolinite (K) was firstly converted to one kind of microporus aluminosilicate (4A) by a green andeconomical method, which was thenacted as the precursor to synthesize two other microporus aluminosilicate (3A and 5A) by ions exchange. After modified and loaded with one kind of rare earth ion (La3+), the final product (A‐La) was then used as synergist to enhance fire retardant property for polypropylene (PP) with intumescent flame‐retardants (IFR). The properties of PP composites for thermal stability and flame retardant were studied and demonstrated that A‐La, especially 4A‐La, had the most obviously flame‐retardant effect. Meanwhile, the macro/micro‐structure of char residues and real‐time fourier transform infrared spectroscopy (FTIR) after heating also showed that A‐La were helpful to promote the formation of homogenous and compact intumescent char layer. This dense carbon layer can effectively control the convection of combustion gases mixture, and heat transfer between underlying matrix and outside environment.  相似文献   

18.
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   

19.
Pentaerythritol diphosphonate melamine-urea-formaldehyde resin salt, a novel cheap macromolecular intumescent flame retardants (IFR), was synthesized, and its structure was a caged bicyclic macromolecule containing phosphorus characterized by IR. Epoxy resins (EP) were modified with IFR to get the flame retardant EP, whose flammability and burning behavior were characterized by UL 94 and limiting oxygen index (LOI). 25 mass% of IFR were doped into EP to get 27.2 of LOI and UL 94 V-0. The thermal properties of epoxy resins containing IFR were investigated with thermogravimetry (TG) and differential thermogravimetry (DTG). Activation energy for the decomposition of samples was obtained using Kissinger equation. The resultant data show that for EP containing IFR, compared with EP, IFR decreased mass loss, thermal stability and R max, increased the char yield. The activation energy for the decomposition of EP is 230.4 kJ mol−1 while it becomes 193.8 kJ mol−1 for EP containing IFR, decreased by 36.6 kJ mol−1, which shows that IFR can catalyze decomposition and carbonization of EP.  相似文献   

20.
In this paper, fumaric acid (FA) which was a new type of environmental and low‐cost flame retardant was applied for thermoplastic polyurethane elastomer (TPU). The flame‐retardant properties of TPU were tested using limiting oxygen index, cone calorimeter test, smoke density test, and thermogravimetric/Fourier transform infrared spectroscopy. It has been proved that FA could improve the difficulty of the ignition of the sample; the limiting oxygen index value of the sample (FA‐4) increased by 29.7% when 2.0 wt% FA was added to TPU. The cone calorimeter test showed that FA can greatly reduce heat release and smoke production during the combustion process of TPU composites. For example, compared with the pure TPU, the peak heat release rate and total smoke release of the sample (FA‐4) with 2.0 wt% FA were decreased by 50.8% and 51.5% respectively. The results of smoke density test showed that the luminous flux of the samples contained 0.5 wt% FA was increased by 79.2% compared with the pure TPU. The TG results revealed that the sample of FA‐4 had higher char residue content compared with the sample of TPU. The results of thermogravimetric/Fourier transform infrared spectroscopy proved that FA could decrease the initial decomposition temperature for TPU composites and increase the release of CO2 and H2O. All results of test illustrated that FA had good flame‐retardant effect on TPU.  相似文献   

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