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1.
In this article, oyster shell powder (OSP) was used as fire safety agent with ammonium polyphosphate (APP) in thermoplastic polyurethane (TPU) composites. The synergistic fire safety improvement between OSP and APP was intensively investigated using limiting oxygen index (LOI), UL‐94, smoke density test (SDT), and cone calorimeter test (CCT). There is a good synergistic effect of reducing the fire hazards when OSP was used with APP in TPU. The peak heat release rate (pHRR) of the sample with 2.0‐wt% OSP and 8.0‐wt% APP decreased to 86.8 kW/m2 from 175.7 kW/m2 of the sample with only 10.0‐wt% APP. The SDT results showed that the luminous flux of sample OSP2/APP8 was up to 28.9% at the end of experiment with flame, which was much higher than that of pure TPU (1.5%). The thermal stability and thermal decomposition of TPU composites were characterized by thermogravimetric analysis/Fourier infrared spectrum analysis (TG‐IR). The result revealed the inert gasses (including CO2 and water vapor) produced by the reaction between OSP and APP. A char formed on the surface of composites, hindered the flame spread, reduced the release of combustible gas, and restricted the precursor of smoke into combustion zone.  相似文献   

2.
At present, thermoplastic polyurethane (TPU) is widely used, but there are still many defects in fire safety, such as burning with heavy smoke and dripping. In this article, OS@MP was synthesized by modifying oyster shell (OS) powder with melamine polyphosphate (MP) and then served as fire‐safe agent for TPU. The fire performance of TPU composites were investigated using microscale combustion colorimeter (MCC), cone calorimeter test (CCT), smoke density test (SDT), and thermogravimetric analysis/Fourier transform infrared (TG‐FTIR) spectrum analysis. The MCC and CCT results revealed that OS@MP could reduce the fire hazards of TPU composites. The peak heat release rate (pHRR) of the sample with 10.0 wt% OS@MP decreased to 170.86 kW/m2 from 1772.37 kW/m2 for pure TPU. And, the SDT results showed that OS@MP could significantly reduce the smoke production of TPU composites. The TG‐FTIR also confirmed that the noncombustible gases (including CO2, ammonia, and water vapor) produced by OS@MP have played a reinforcing role in TPU composites as well as a char formed on the surface of composites, which could act as a barrier to prevent the heat and air, reinforce the fire safety of TPU.  相似文献   

3.
A comparison of melamine salt of pentaerythritol phosphate (MPP), and a synergistic agents, iron–graphene (IG) was performed in thermoplastic polyurethane (TPU) by masterbatch‐melt blending on thermal and flame retardant properties. The flame retardant properties of TPU composites were characterized by limiting oxygen index (LOI), UL 94 and cone calorimeter test (CCT). The CCT results revealed that IG can significantly enhance flame retardant properties of MPP in TPU. The peak heat release rate of neat TPU and flame retardant TPU/MPP composites decreased from 2192.6 and 226.7 to 187.2 kW/m2 compared with that of TPU containing 0.25 wt% IG. The thermal stability and thermal decomposition of TPU composites were characterized by thermogravimetric analysis (TGA) and thermogravimetric/Fourier infrared spectrum analysis (TG‐IR). The results indicated IG and MPP can improve the thermal stability of TPU. The formation of thermal conductive network by IG can promote the decomposition of MPP into nonflammable melt, which can play the role of heat barrier and restrict the diffusion of fuels into combustion zone and access of oxygen to the unburned fuels. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

4.
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   

5.
Phosphorus tailings and fly ash both are solid wastes and do harm to the environment. Here, they were added into thermoplastic polyurethane (TPU) matrices together with intumescent flame retardants (IFR), and the synergistic effects between IFR and phosphorus tailings or fly ash for improving the flame retardancy of TPU were investigated. The cone calorimeter test (CCT) results indicated that adding phosphorus tailings or fly ash substitute for part of IFR could obtain a better flame retardant effect. The peak heart release rate (PHRR) of TPU/25 wt% IFR composites exhibited a reduction of 77% than that of neat TPU, and the total smoke production presented a reduction of 16%. However, the PHRR value and total smoke production of the sample TPU/20 wt% IFR/5 wt% phosphorus tailings were reduced by 91% and 57%, respectively, compared to that of neat TPU. The dense char promoted by the presence of IFR and phosphorus tailings or fly ash delayed the diffusion of volatile pyrolysis products and transmission of heat and oxygen to the underlying material. Therefore, a certain amount of phosphorus tailings or fly ash can be used as synergistic agents with IFR to enhance the fire safety of TPU materials. From another aspect, it also provides a promising way for recycling use of phosphorus tailings and fly ash.  相似文献   

6.
APP@ETA, as a new type of flame retardant, was prepared by chemically modifying ammonium polyphosphate (APP) with ethanolamine (ETA) and applied to thermoplastic polyurethane (TPU) in this study. Then, the smoke suppression properties and flame‐retardant effects of APP@ETA in TPU composites were evaluated using smoke density test, cone calorimeter test, etc. And, the thermal degradation properties of flame‐retardant TPU composites were investigated by thermogravimetric analysis/infrared spectrometry. The smoke density test results indicated that APP@ETA could obviously improve the luminous flux of TPU composites in the test with or without flame. The cone calorimeter test results showed that total smoke release, smoke production rate and smoke factor of the composites with APP@ETA were significantly decreased than those of the composites with APP. For example, when the loading of APP@ETA or APP was 12.5 wt%, the total smoke release of the sample with APP@ETA decreased to 3.5 m2/m2 from 6.0 m2/m2, which was much lower than that of the sample with APP, reduced by 41.7%. The thermogravimetric analysis results demonstrated that APP@ETA could decrease the initial decomposition temperature and improve the thermal stability at high temperature for TPU composites. Copyright © 2017 John Wiley & Sons, Ltd.  相似文献   

7.
Metal‐organic framework MIL‐53 (Fe)@C/graphite carbon nitride hybrid (MFeCN), a novel flame retardant, was synthesized by hydrothermal reaction and subsequently added into unsaturated polyester resin (UPR). The structure, morphology, and thermal stability of MFeCN were characterized by Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy‐dispersive X‐ray spectroscopy (EDS), and thermogravimetric analysis (TG). The thermal stability and flammability of the UPR composites were characterized by TG and cone calorimeter tests (CCT). The results of CCT demonstrated that the peak heat release rate (pHRR), total heat release (THR), peak smoke production rate (pSPR), and total smoke production (TSP) of UPR/MFeCN‐4 were reduced by 39.8%, 10.2%, 33.3%, and 14.5%, respectively, comparing with UPR. The results of TG and CCT indicated that MFeCN could improve the thermal stability, flame retardancy, and smoke suppression properties of the UPR composites. The residues after CCT were then characterized by laser Raman spectroscopy (LRS), XPS, and SEM. Finally, based on the above experimental results and analysis, the flame retardancy mechanism of MFeCN was proposed.  相似文献   

8.
It is mainly studied that the smoke-suppression properties and synergistic flame-retardant effect of hollow glass microsphere (HM) in flame retardant thermoplastic polyurethane (TPU) composites based on ammonium polyphosphate (APP) as a flame-retardant. Also, the smoke suppression properties and flame-retardant effect were investigated by smoke density test (SDT), cone calorimeter test (CCT), limiting oxygen index, and thermogravimetric analysis, separately. The char residues left after CCT were examined by scanning electron microscopy. The data of SDT shows that HM could effectively decrease smoke production of TPU composites. The results of CCT reveal that the system of APP/HM could reduce heat release rate, smoke production rate, and total smoke release. It is shown that APP/HM is a good system with smoke-suppression and synergistic flame-retardant properties in flame-retardant TPU composites.  相似文献   

9.
In this paper, a new type of flame retardant (AF‐Fe) based on para‐aramid fiber (AF) which was modified with iron diethyl phosphinate was applied for thermoplastic polyurethane elastomer (TPU). The flame‐retardant properties of TPU were tested using cone calorimeter test, smoke density test, and thermogravimetric analysis/infrared spectrometry. The cone calorimeter test showed that AF‐Fe can greatly reduce the heat release rate, total heat release, smoke factor, and other parameters of TPU composites compared with the sample of TPU/AF. For example, the pHRR of the composite with 1.0 wt% AF‐Fe was reduced by 15.19% compared with the sample with the same content of pure AF. In addition, the smoke factor of TPU/AFFe3 was reduced by 50.52% and 15.63% compared with TPU0 and TPU/AF respectively. The results of smoke density test showed that the luminous flux of TPU/AFFe3 was increased by 79.26% compared with the sample of TPU/AF. The TG results revealed that the sample with TPU/AFFe3 had lower weight loss rate and higher char residue content at 700°C compared with the sample of TPU/AF.  相似文献   

10.
In this work, phosphorylated chitosan‐coated carbon microspheres (PCH@CMS) was successfully synthesized. Obtained PCH@CMS used as flame retardant was added into unsaturated polyester resin (UPR). Fourier infrared spectroscopy (FTIR) and X‐ray electron spectroscopy (XPS) results indicated that C═O, P─O, and P═O appeared on the surface of PCH@CMS. Compared with UPR, the residues of UPR/PCH@CMS‐10 at 800°C under nitrogen and air atmospheres increased by 9.0 and 3.9 wt%, respectively, and the peak heat release rate (pHRR) and the peak smoke release rate (pSPR) of UPR/PCH@CMS‐3 decreased by 18.9% and 23.5%, respectively. Limiting oxygen index (LOI), thermogravimetric analyzer (TG), and cone calorimeter test (CCT) results showed that the addition of PCH@CMS could enhance the flame retardancy and smoke suppression of the UPR composites. Moreover, the residues after CCT were characterized by scanning electron microscopy (SEM), XPS, and laser Raman spectroscopy (LRS). Based on the above results, the flame retardant mechanism of PCH@CMS was proposed. The carbon layer produced by the UPR/PCH@CMS composites was tortuous and could suppress the heat and pyrolysis product exchange with UPR matrix.  相似文献   

11.
In this work, a new type of leaf‐shaped cobalt‐zeolitic imidazolate framework–modified graphene (Co‐ZIF‐L@RGO) hybrid was successfully prepared and blended with an intumescent flame retardant (IFR). It was added into thermoplastic polyurethane (TPU) to study the effect of its combination with IFR on the thermal conductivity and flame retardant performance of TPU. The morphology and structure of the Co‐ZIF‐L@RGO hybrid were characterized by scanning electron microscope (SEM), Fourier transform infrared and X‐ray diffraction (XRD). The results showed that Co‐ZIF‐L were uniformly loaded on the surface of graphene. Furthermore, compared with pure TPU, the limiting oxygen index values of the composite material with 3 wt% Co‐ZIF‐L and 27 wt% IFR increased to 32.6%. Their UL‐94 rating reached V‐0 rating. Their peak heat release rate, total heat release, peak smoke production rate and total smoke production were also greatly reduced by 84.4%, 70.1%, 60.3% and 62.5%, respectively. The thermogravimetric‐infrared test results showed that the amount of toxic gas emissions was effectively suppressed. The residual carbon was analyzed by SEM, laser Raman spectroscopy and XRD, and flame retardant mechanism was further investigated. Besides, the addition of this hybrid improved the thermal conductivity of TPU.  相似文献   

12.
Three novel phosphorus‐containing Salen‐based derivatives (Salen‐DPCP‐M: M = Ni, Zn, and Mn), which include both phenyl phosphate structures (DPCP) and Salen‐metal complexes, were prepared for enhancing the fire safety of thermoplastic polyurethane (TPU). Thermogravimetric analysis (TGA) showed that Salen‐DPCP‐M altered the thermal degradation pathways of TPU probably due to the phosphorus‐containing structure of Salen‐DPCP‐M. The cone calorimeter test showed that the addition of 3 wt% of Salen‐DPCP‐Ni, Salen‐DPCP‐Zn, and Salen‐DPCP‐Mn lowered the peak of heat release rate (PHRR) from 1495 kW/m2 for neat TPU to 690, 875, and 813 kW/m2, respectively, for the TPU composites, which demonstrated that Salen‐DPCP‐M improved the fire safety of TPU. In addition, the release of toxic CO gas from the Salen‐DPCP‐Ni/TPU and Salen‐DPCP‐Zn/TPU composites was reduced by 78.2% and 80.0%, respectively. The results of TGA/infrared spectrometry (TG‐FTIR) showed that the incorporation of Salen‐DPCP‐Ni promoted the release CO2, while reducing the formation of harmful gases. Laser Raman spectroscopy (LRS) and scanning electron microscopy (SEM) showed that Salen‐DPCP‐Ni/TPU and Salen‐DPCP‐Zn/TPU composites formed a dense and stable char layer. Herein, the mechanism of these flame retardants containing novel phosphorus‐containing Salen‐metal complexes is also proposed.  相似文献   

13.
ZHS@ Mg‐Al‐LDH and ZHS@α‐ZrP hybrid materials were prepared by electrostatically loading zinc hydroxystannate (ZHS) on the layered compounds (Mg‐Al‐LDH and α‐ZrP) in this work. With the addition of 2 wt% of the two hybrid materials to epoxy resin (EP), respectively, the fire hazard of EP and its composites were investigated. The limiting oxygen index (LOI) of ZHS@ Mg‐Al‐LDH/EP composite increased by 19.0% compared with pure EP, while its peak heat release rate (PHRR), total heat release rate (THR), and peak smoke release rate (SPR) decreased by 48.2%, 20.8%, and 21.6%, respectively, evidenced by the results of the LOI test and cone calorimetry test (CCT). The LOI of ZHS@α‐ZrP/EP composite increased by 20.4%, and its PHRR, THR, and SPR decreased by 47.7%, 21.4%, and 27.1%, respectively. Both hybrid materials showed prominent flame retardant and smoke suppressing properties. In addition, through the analysis of the TG‐IR and Raman spectrum of residual char, the specific mechanism of flame retardance and smoke suppression was explored.  相似文献   

14.
The massive accumulation of phosphorus tailings (PT) not only occupies land resources and also causes great threat to ecological environment and human security. It is of great significance to explore the resource utilization of PT in some fields. Herein, aluminum hypophosphite (AHP) and PT are blended together to enhance the flame retardancy of thermoplastic polyurethane (TPU) composites, and the synergistic effects between AHP and PT are investigated systematically. Cone calorimeter test (CCT) results indicate that the peak heat release rate (PHRR) and total heat release (THR) of the samples containing 25 wt% AHP are decreased by 89% and 68%, respectively, and the total smoke release (TSR) show a reduction of 58.8%, in comparison with those of neat TPU. For the sample TPU/22.5AHP/2.5PT, the PHRR, THR, and TSR are decreased by 91.2%, 70%, and 63%, respectively. Scanning electron microscopy (SEM) analysis results demonstrate that the addition of PT can facilitate the generation of dense and compact char layers, preventing the release of heat and smoke effectively. All the abovementioned results indicate that the synergistic effects are existed between AHP and PT for enhancing the fire safety of TPU composites, which can provide a new way for the utilization of PT.  相似文献   

15.
The objective of the study was to investigate the effect of the organo‐modified nanosepiolite (ONSep) on improving the fire safety of polypropylene (PP). The composites based on PP, flame retardant master batch (MB‐FR, 25 wt% PP+50 wt% decabromodiphenyl ether (DBDPE)+25% antimony trioxide (ATO)) and ONSep were prepared via melt blending. The results of the limiting oxygen index (LOI) and vertical burning rating (UL‐94) test indicated that PP/40 wt% MB composites had no rating with seriously dripping phenomenon, while the LOI value was only 22.5. However, as 4 wt% ONSep was added in PP/40 wt% MB composites, the composites achieved UL94 V‐0 rating and the LOI value was 24.3. In comparison, PP/50 wt% MB composites could not reach the V‐0 rating either. The TGA results revealed that the addition of ONSep enhanced the thermal stability of the PP/MB‐FR composites. The cone calorimeter results indicated that the heat release rate, average mass loss rate, smoke production rate and smoke temperature of the PP/40 wt% MB‐FR/4 wt% ONSep composites decreased in comparison with those of PP/40 wt% MB‐FR composites. Simultaneously, the Young modulus and impact strength were also much better improved with the increase of ONSep loading. Therefore, the synergistic flame retardancy of ONSep in PP/MB‐FR matrix significantly containing a halogen based flame retardant (DBDPE) significantly improved the fire safety and mechanical properties of the composites, and allowed to decrease the total amount of brominated fire retardants.  相似文献   

16.
A novel zeolitic imidazolate framework (ZIF‐8) nanoparticles@polyphosphazene (PZN) core‐shell architecture was synthesized, and then, ZIF‐8@PZN and ammonium polyphosphate (APP) were applied for increasing the flame retardancy and mechanical property of epoxy resin (EP) through a cooperative effect. Herein, ZIF‐8 was used as the core; the shell of PZN was coated to ZIF‐8 nanoparticles via a polycondensation method. The well‐designed ZIF‐8@PZN displayed superior fire retardancy and smoke suppression effect. The synthesized ZIF‐8@PZN observably raised the flame retardancy of EP composites, which could be demonstrated by thermogravimetric analysis (TGA) and a cone calorimeter test (CCT). The chemical structure of ZIF‐8@PZN was characterized by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). Compared with pure epoxy, with the incorporation of 3 wt% ZIF‐8@PZN and 18 wt% APP into the EP, along with 80.8%, 72.6%, and 64.7% decreased in the peak heat release rate (pHRR), the peak smoke production rate (pSPR), and the peak CO production rate (pCOPR), respectively. These suggested that ZIF‐8@PZN and APP generated an intumescent char layer, and ZIF‐8@PZN can strengthen the char layer, resulting in the enhancement in the flame resistance of EP.  相似文献   

17.
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   

18.
A series of flame-retardant ethylene–vinyl acetate (EVA) composites with different contents of aluminum phosphate (AHP) and Trimer were prepared. The synergistic flame-retardant effects of the Trimer with AHP in EVA/AHP blends were studied by limiting oxygen index (LOI) tests, UL-94 tests, cone calorimeter tests, thermogravimetric analysis, and scanning electron microscopy (SEM). The LOI and UL-94 results showed that the system containing AHP and Trimer was very effective in improving the flame retardancy of EVA. When the mass ratio of AHP and Trimer was 3:1, the highest flame retardancy could be obtained, and when the flame-retardant loading was 30 wt%, the EVA/AHP/Trimer (7.5%) sample could achieve the V-0 rating in UL-94 tests, at the same time, its LOI value was 24.4%. The TG and DTG results showed that the addition of flame retardants catalyzes EVA decomposition in the first stage and generates a more stable char residue in the second stage. Consequently, an efficient reduction in the flammability parameters, such as heat release rate, total heat release, smoke production rate, and total smoke production could be observed. In addition, it was observed from the SEM observations of the morphological features that the AHP and Trimer combination, at the optimum proportion, could promote the formation of compact charred layers and prevent their cracking, which effectively protected the underlying materials from burning.  相似文献   

19.

The flammability and droplet properties of thermoplastic polyurethane (TPU) have limited its wide application in many fields. In this article, isopropyl tris(dioctylphosphoryloxy) titanate was selected as synergism and compatilizer with oyster shell powder as flame retardant in TPU composites. And the influence of isopropyl tris(dioctylphosphoryloxy) titanate for flame-retardant TPU composites has been intensively investigated using the smoke density test, the cone calorimeter test, and the thermogravimetric analysis/infrared spectrometry, respectively. The test results show that isopropyl tris(dioctylphosphoryloxy) titanate can reduce the smoke production and heat release. And the total smoke production was reduced by 32% when the mass fraction of isopropyl tris(dioctylphosphoryloxy) titanate was 0.1%. The above results indicate that isopropyl tris(dioctylphosphoryloxy) titanate has a good application prospect in reducing the risk of TPU combustion.

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20.
《中国化学快报》2023,34(1):107202
A new biobased flame retardant (MHPA) with remarkable compatibility was synthesized via a facile and low-cost neutralization reaction of magnesium hydroxide (MH) and phytic acid (PA). By blending the prepared MHPA into ethylene vinyl acetate (EVA), the fire retardancy, smoke suppression and mechanical properties of the composites were significantly improved. When 50 wt% of MH was added into EVA matrix, the value of limiting oxygen index (LOI) reached 26.1%. Whereas, when 10 wt% MH in the EVA composites (with initial 50 wt% MH) was replaced by MHPA, the resulted EVA composites had a LOI value of 30.8%, indicating high efficiency of addition of MHPA to improve flame retardancy. Moreover, the heat release rate (HRR) and total smoke production (TSP) of the EVA composites reduced by 54.4% and 27.6%, respectively, suggesting that incorporation of MHPA could effectively hinder rapid degradation of EVA composites during burning process. The fire-retardant mechanism may reside in that the MHPA combined with MH can present the excellent carbonization and expansion effects. This study illustrates that the biobased MHPA has a broad application prospect to develop flame-retardant EVA composites.  相似文献   

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